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Deem, Madeleine C. ; Hein, Jason E. ; DOI: PubMed ID:

Abstract: Online HPLC reaction progress monitoring provides detailed data-rich profiles; however, extracting kinetic information requires UV-visible response factors to determine concentrations from peak areas. If the reaction's overall mass balance is known and some anal. trend for all relevant species can be recorded, it is possible to estimate the absolute response factors of all species using a system of linear equations. We delineate a method using the Microsoft Solver plug-in to convert time course profiles to reagent concentrations without anal. standards

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Product Details of [ 1754-62-7 ]

CAS No. :1754-62-7 MDL No. :MFCD00008458
Formula : C10H10O2 Boiling Point : -
Linear Structure Formula :- InChI Key :CCRCUPLGCSFEDV-BQYQJAHWSA-N
M.W : 162.19 Pubchem ID :637520
Synonyms :
Methyl (E)-3-phenylpropenoate

Safety of [ 1754-62-7 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1754-62-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 1754-62-7 ]

[ 1754-62-7 ] Synthesis Path-Downstream   1~46

  • 1
  • [ 103-26-4 ]
  • [ 141-43-5 ]
  • [ 35241-61-3 ]
YieldReaction ConditionsOperation in experiment
87% With sodium carbonate In methanol at 80℃; for 2h; regioselective reaction; GeneralProcedure 2 for Amidation of Esters 1a-1h General procedure: To a solution of esters1a-1h (1.0 mmol) in MeOH (1.0 mL), Na2CO3(106 mg, 1.0 mmol) and aminoalcohol 2(5.0 mmol) were added. The reactionmixture was stirred at 80 °C for 1.25-8 h. The resultant reaction mixture was cooled to roomtemperature, diluted with MeOH (10.0 mL) and filtered. The filtrate was thenconcentrated under reduced pressure. The viscous residue, thus obtained, waspurified by column chromatography on silica gel to obtain the correspondingcinnamamides
at 100 - 120℃;
  • 2
  • [ 103-26-4 ]
  • [ 103-25-3 ]
YieldReaction ConditionsOperation in experiment
100% With hydrogen In ethyl acetate at 25℃; for 1h;
100% With hydrogen In tetrahydrofuran at 20℃; for 1h; atmospheric pressure;
100% With hydrogen In tetrahydrofuran at 25℃; for 1h;
100% With C35H25ClF18N3Rh*CH4O In isopropyl alcohol at 82℃; for 24h;
99% With ammonium formate; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate at 150℃; for 1.33333h; microwave irradiation;
99% With hydrogen In water at 25℃; for 24h;
99% With hydrogen In ethyl acetate at 80℃; for 0.05h; microwave irradiation;
99% With hydrogen; ammonium formate In ethanol at 140℃; for 0.0833333h; microwave irradiation;
99% With hydrogen In ethyl acetate at 20℃; Flow reactor; Green chemistry; chemoselective reaction;
98% With hydrogen In ethanol for 0.666667h;
97% With ammonium formate; silica gel; palladium dichloride In formic acid; water for 0.1h; microwave irradiation;
97% With hydrogen In tetrahydrofuran for 24h;
95% With hydrido(triphenylphosphine)copper(I) hexamer; phenylsilane In toluene for 0.333333h; Ambient temperature;
95% With hydrogen In water at 20℃; for 1h; Green chemistry; 4.6.1. General procedure for hydrogenations General procedure: 1.0 mmol, 0.148 g), catalyst BPPd(0)Si (5 mol%, 0.0836 g), andKOH (1.0 equiv., 5 mL 0.2 M solution) were added to the reactionflask under hydrogen gas (1 atm). The reaction mixture was stirredat room temperature for 30 min followed by catalyst filtration andwashing with 10 mL of water and ethyl acetate. The pH was adjusted to 2e3 using 1 N HCl. The organic phase was collectedafter solvent extraction from ethyl acetate and dried over MgSO4and in vacuo. The product was purified by silica-gel column chromatographyand analyzed by 1H NMR spectroscopy.
94% With N,N,N,N,N,N-hexamethylphosphoric triamide; methylcopper; diisobutylaluminium hydride In tetrahydrofuran; diethyl ether; hexane at -50℃; for 1h;
94% With maghemite-palladium nanocomposite; hydrogen In ethanol at 70℃; for 0.0125h;
91% With 5%-palladium/activated carbon; hydrogen In methanol
90% With Amberlite IRA 938-supported formate In dimethyl sulfoxide for 0.00833333h; microwave irradiation;
90% With magnesium; zinc(II) chloride for 0.333333h;
89% With sodium tetrahydroborate; copper(ll) sulfate pentahydrate; cobalt(II) chloride hexahydrate In methanol at 20℃; for 0.333333h; General hydrogenation procedure General procedure: The catalyst precursor in form of a 0.04 M CuSO4 and 0.004 M CoCl2 solution was added to a solution of the alkene/alkyne compound in methanol. The reaction was started by adding an initial portion of NaBH4, resulting in a color change to black (in situ prepared catalyst) and vigorous gas evolution. Additional portions of NaBH4 were added in intervals of typically three or four minutes. The reaction itself was carried out at room temperature and normal atmosphere. However, generation of heat due to the exothermic character of the reaction usually heated the reaction mixture to 30-40 °C. Cooling is generally not necessary in small scale. For large scale reactions a reflux condenser was used. The higher reaction temperature did not influence the reaction yield. The reaction mixture was finally quenched by adding 2 M H2SO4. Work up was carried out by extracting the water/methanol phase with DCM. The catalyst in general stays within the water/methanol layer. Drying the DCM layer with MgSO4 followed by filtration removes all remaining catalyst particles. The drying agent was filtered of and the DCM was removed in vacuo.
87% With sodium tetrahydroborate; hydrogen; nickel dichloride In isopropyl alcohol at 50℃; for 8h; Reduction of oct-1-ene (1). General procedure: Anhydrous nickel(II) chloride, 1.75 g (14 mmol), was added to a suspension of 1.1 g (30 mmol) of NaBH4 in 20 mL of propan-2-ol to obtain a black colloidal solution. Hydrogen was passed through the solution at a flow rate of 15-20 mL/min, 34 g (0.3 mol) of oct-1-ene (1) was added, and the mixture was stirred for 6 h at 50-60 °C. The mixture was cooled, 1 mL of water was added to accelerate coagulation of the catalyst, the precipitate was filtered off, the solvent was removed from the filtrate by distillation through a column, and the residue was distilled. Yield 28 g (0.246 mol, 82%), bp 124-127°C[20]. Mass spectrum, m/z (Irel, %): 114 (5) [M]+, 85(25), 71 (20), 57 (33), 43 (100).
87% With methanol; (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate at 20℃; for 16h; Inert atmosphere; Irradiation; Sealed tube;
86% With hydrogen In tetrahydrofuran Ambient temperature; atmospheric pressure;
86% With sodium tetrahydroborate; nickel dichloride In methanol; water at 20℃; for 0.5h;
82% With hydrogen; palladium diacetate In ethanol at 20℃;
81% With hydrazine hydrate In ethanol at 70℃; for 8h;
81% With 1,3-di-tert-butyl-2-(neopentyloxy)-2,3-dihydro-1H-1,3,2-diazaphosphole; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In acetonitrile at 40℃; for 12h; Glovebox; Inert atmosphere;
80% With diphenylsilane; zinc(II) chloride In chloroform for 48h; Ambient temperature;
80% With dicobalt octacarbonyl; water In 1,2-dimethoxyethane for 2h; Heating;
18% With 2-phenylthiazoline In methanol at 80℃; for 3h;
5% With N-propyl-1,4-dihydronicotinamide; lithium perchlorate In acetonitrile at 70℃; var.: MeOH, 60 deg C;
With formic acid; triethylamine for 8h; Heating; further catalysts;
With nickel at 100℃; Hydrogenation;
With TEA In methanol at 25℃; for 8h; Irradiation;
With methanol; magnesium for 2h; Ambient temperature; Yield given;
99 % Chromat. With hydrogen In diethyl ether at 25℃;
With methanol; sodium tetrahydroborate In tetrahydrofuran at 30℃; for 1h;
With water; nickel dichloride; zinc In 1,4-dioxane at 39.9℃; Irradiation;
With hydrogen In ethyl acetate for 16h;
With hydrogen In methanol for 3h; Ambient temperature;
With dihydrogen peroxide; tetrabutylammonium borohydride 1.) CHCl3, reflux, 5 h, 2.) H2O; Yield given. Multistep reaction;
With ethylene dimethylacrylate-based polymer; hydrogen In toluene at 108℃;
With hydrogen In tetrahydrofuran
99 % Chromat. With ammonium formate; 1-butyl-3-methylimidazolium Tetrafluoroborate at 65℃; for 5h;
99 % Chromat. With methanol; samarium(II) dibromide In tetrahydrofuran at 180℃; for 0.0833333h; microwave irradiation;
With hydrogen; sodium docusate In hexane at 30℃; for 0.1h;
With samarium diiodide; N,N,N,N,-tetramethylethylenediamine; water In tetrahydrofuran at 20℃;
With hydrogen In ethanol at 25℃;
99 % Chromat. With ammonium formate; 1-butyl-3-methylimidazolium Tetrafluoroborate at 80℃; for 5h;
With hydrogen In isopropyl alcohol at 20℃; for 0.25h;

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  • 3
  • [ 100-52-7 ]
  • [ 96-34-4 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
92% With triphenylphosphine In N,N-dimethyl-formamide at 20℃; for 26h;
68% With diphenylsilane; sodium carbonate; 3-methyl-1-phenyl-2,3,4,5-tetrahydro-1H-phosphole-1-oxide In toluene at 100℃; for 24h; Inert atmosphere; stereoselective reaction;
68% With diphenylsilane; sodium carbonate; 3-methyl-1-phenyl-2,3,4,5-tetrahydro-1H-phosphole-1-oxide In toluene at 100℃; for 24h; Inert atmosphere;
With magnesium; mercury dichloride
With zinc/copper couple; toluene; benzene Erhitzen des Reaktionsprodukts mit wss. Oxalsaeure;
With sodium hydride; phosphonic acid diethyl ester 1.) DME, 2.) 1 h; Yield given. Multistep reaction;

  • 4
  • [ 103-26-4 ]
  • [ 62788-55-0 ]
YieldReaction ConditionsOperation in experiment
65% With sodium periodate; sodium hydrogensulfite In water; acetonitrile at 30℃; for 39 - 40h; a.iii EXAMPLE (iii); Synthesis of (+/-)-methyl 3-hydroxy-2-iodo-3-phenylpropanoate of formula 2 where x=l and R'=CH3. EXAMPLE (iii); Synthesis of (+/-)-methyl 3-hydroxy-2-iodo-3-phenylpropanoate of formula 2 where x=l and R'=CH3. [0039] To a stirred suspension of methyl cinnamate(3g, 20 mmol), HIO4.2H2O (5.2 g, 24 mmol) 12 ml water and 40 ml of acetonitrile, 1M sodium bisulphite solution (5.2 g in 50 ml) was added to the above mixture over a period of three-four hours with stirring and at 30° C. The reaction mixture was further stirred for 36 hrs till the reaction was complete (TLC monitored). The resulting solution was extracted with ethyl acetate (3×50 ml), and combined organic layer was washed with aqueous sodium sulphite followed by drying over anhydrous sodium sulphate. The contents concentrated in vacuo to give a crude material, which was purified by crystallization (benzene: hexane, 1:1) to furnish compound of formula 2 m.pt 63° C., yield 3g (65%). [0040] 1HNMR(CDCl3) δ: 7.35(5H, s, Ar-H), 5.05(1H, d, J=8.42 Hz, CH-OH), 4.55(1H, d, J=8.43 Hz, CH-Br), 3.75(3H, s, CH3).
With iodine; silver(I) acetate In sulfolane; chloroform
  • 5
  • [ 75-52-5 ]
  • [ 103-26-4 ]
  • [ 34687-03-1 ]
YieldReaction ConditionsOperation in experiment
96% With N,N,N',N'-tetramethylguanidine for 3h; Heating;
85% With N,N,N',N'-tetramethylguanidine at 20℃; for 48h;
85% With 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3, 2-diazaphosphorine supported on polystyrene at 30℃; for 18h;
82% With N,N,N',N'-tetramethylguanidine at 20℃; for 42h; 4.1.1. Methyl 4-nitro-3-phenylbutanoate (2) Methyl trans-cinnamate 1 (5.01 g, 30.9 mmol) was weighed intoa 250 mL round-bottom flask with a magnetic stir-bar and dissolved in nitromethane (17 mL, 0.308 mol), to which stirringcommenced. 1,1,3,3-tetramethylguanidine (775 mL, 6.18 mmol) wasadded, and the mixture was left to stir for 42 h at room temperature,checking for completion with TLC. After completion, themixture was quenched with 5% HCl (75 mL) and washed withdiethyl ether (3 x 75 mL). The organic layers were combined, driedwith MgSO4, filtered and concentrated under reduced pressure toafford an orange-coloured oil. The oil was then purified using columnchromatography (Mobile phase: 10% EtOAc in petroleum benzine, TLCs were checked in 20% EtOAc in petroleum benzine) toafford 2 (5.62 g, 82%) as a clear oil. 1H NMR (400 MHz, CDCl3)d 7.37e7.21 (m, 5H), 4.70 (ddd, J 20.5, 12.6, 7.5 Hz, 2H), 3.99(quint, J 7.4 Hz, 1H), 3.64 (s, 3H), 2.83e2.74 (m, 2H) ppm. 13C NMR(101 MHz, CDCl3) d 171.2, 138.4, 129.2, 128.2, 127.4, 79.5, 52.1, 40.3,37.6 ppm.
59% With 1,1,3,3-tetramethylguanidine at 90℃; for 6h; 11 Example 11; 3-Methyl-2-(3-phenyl-pyrr'olidin- l-yl)'6'pyrid.in-4-yl-3H-pyrimidin-4-one hydrochloride (Compound No. Dl); 4-Nitro-3-phenvl-butvric acid methyl ester; A solution of methyl cinnamate (4.93 g, 30.4 mmol) and teteramethylguanidine (3.99g, 34.6 mmol) in nitromethane (30 ml) was stirred for 6 hours at 90 0C. After removal of the solvent under reduced pressure, the residue was partitioned between water and ethyl acetate, and the organic layer was. washed with water and brine and then dried over sodium sulfate. The organic solvents were removed under reduced pressure, and the residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate = 4/1) to afford 4-nitro"3-phenyl-butyric acid methyl ester (4.02 g, 59 %)
With N,N,N',N'-tetramethylguanidine at 70℃;
With 1,8-diazabicyclo[5.4.0]undec-7-ene In methanol
With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃;

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  • 6
  • [ 103-26-4 ]
  • [ 100-51-6 ]
  • [ 103-41-3 ]
YieldReaction ConditionsOperation in experiment
96% With iron(III)-acetylacetonate; In n-heptane; at 105℃; for 10h;Inert atmosphere; General procedure: To a dry 25 mL, bottomed flask equipped with a Dean-Stark trap containing a plug of 4A molecular sieves (pellets) and topped with a reflux condenser was added of Fe(acac)3 ( 36 mg, 0.10 mmol, 5 mol%) and a solution of methyl bezoate (272 mg, 256 .L, 2.0 mmol), benzyl alcohol (216 mg, 208 .L, 2.0 mmol) and triphenyl methane (488 mg, 2 mmol, as internal standard) in heptane (20 mL). The mixture was heated to reflux (105 C) for an indicated time periods. After completion of the reaction as monitored by TLC, 1H NMR and GC, the reaction mixture was cooled to room temperature and the solvent was evaporated. The crude product was purified by column chromatography on silica gel to afforded benzyl benzoate 403 mg, 95% yield. The product obtained was characterized by 1H, 13C NMR, ESI-MS or GC-MS spectroscopic methods. The conversions of the products determined by GC are based on triphenyl methane as an internal standard and are response-corrected based on authentic samples.
  • 7
  • [ 103-26-4 ]
  • [ 122-97-4 ]
YieldReaction ConditionsOperation in experiment
99% With C17H16BrMnNO3P; potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 100℃; for 6h; Autoclave; chemoselective reaction;
91% With hydrogen; C28H25BrMnN2O2P; lithium tert-butoxide In propan-1-ol at 100℃; for 24h; Autoclave;
87% With sodium tetrahydroborate; [fac-8-(2-diphenylphosphinoethyl)amidotrihydroquinoline]RuH(PPh)3(CO); hydrogen In tetrahydrofuran at 120℃; for 18h; Inert atmosphere; Autoclave;
100 % Chromat. With lithium aluminium tetrahydride In tetrahydrofuran for 0.166667h; Ambient temperature;
With sodium tetrahydroborate; [fac-8-(2-diphenylphosphinoethyl)amidotrihydroquinoline]RuH(PPh3)(CO); hydrogen In tetrahydrofuran at 120℃; for 18h; Autoclave; Industrial scale; 4-9 Example 4-9 General procedure: (1 mmol) of NaBH44, 3.08 g (20 mmol, S: B: C: 2000: 20: 1) of methyl o-fluorobenzoate were sequentially added to 100 mL of a glass bottle in a ratio of 7.51 mg ),The reaction system was placed in a 100mL autoclave, replaced with hydrogen three times, rushed into hydrogen 50atm, temperature set at 120 , heating and stirring reaction 18 hours, the reactor was placed in an ice bath to room temperature, venting gas .GC analysis of the reaction solution specific results in Table III. Except that 3.24 g of methyl acrylate (methyl cinnamate) was used instead of methyl o-fluorobenzoate (Example 3-1) and heated and stirred for 18 hours. GC analysis of the reaction solution, the results shown in Table IV.

  • 8
  • [ 103-26-4 ]
  • [ 140-10-3 ]
YieldReaction ConditionsOperation in experiment
97% With sodium hydroxide In water 4 mPEG5K Cinnamic Acid (Compound 6a) Example 4 mPEG5K Cinnamic Acid (Compound 6a) To a solution of mPEG5K cinnamic acid methyl ester (compound 5a, 37.6 g, 7.26 mmol) in 300 mL of water was added a solution of sodium hydroxide (0.58 g, 14.5 mmol) in 80 mL of water. This mixture was stirred overnight at room temperature, followed by acidification of the reaction mixture with HCl, and extraction with DCM. The combined DCM layers were dried over anhydrous sodium sulfate and filtered. The solvent was then partially removed on the rotovap and the product was precipitated with ether, and collected and washed with ether to give 36.4 g of product in 97% yield: 13C NMR (75.4 MHz, CDCl3) δ 168.22, 160.08, 144.42, 129.25, 126.75, 115.11, 114.50, 71.54-67.16 (PEG), 58.65.
90% With bis(tri-n-butyltin)oxide In benzene at 80℃; for 24h;
90% With bis(tri-n-butyltin)oxide In benzene at 80℃; for 24h;
86% With potassium carbonate; thiophenol In 1-methyl-pyrrolidin-2-one at 190℃; for 0.166667h;
80% With phosphate buffer; Bacillus sublilis esterase In methanol; hexane at 37℃; for 24h;
80% With sulfuric acid; pyrographite In water at 100℃; for 48h; General procedure for the acidic hydrolysis of ester 1 mediated by activated charcoal General procedure: Aqueous 3M H2SO4 (2.0 mL) was added to a mixture of ester 1b (272 mg, 2.0 mmol) and activated charcoal (400 mg) in a 10 mL flask. The mixture was stirred at 700 rpm at room temperature for 3 minutes. After stirring at 400 rpm at 100 °C for 24 h, Et2O (10 mL) was added. Activated charcoal was removed by filtration and washed with ether. The aqueous phase was extracted with ether three times and the combined ethereal solution was washed with water (2 mL×2), dried, and evaporated. The residue was purified by column chromatography on silica gel using heptane-acetone (3 : 1) as eluent to give 2b (205 mg, 84%).
72% With sodium hydroxide In ethanol; water at 20℃; for 16h;
70% With potassium fluoride; thiophenol In various solvent(s) at 190℃; for 0.166667h;
70% With potassium fluoride; thiophenol In 1-methyl-pyrrolidin-2-one for 0.166667h; Heating;
50% With hydrotalcite; dihydrogen peroxide In methanol at 20℃; for 7h;
With sodium hydroxide for 2h; Heating; Yield given;
With potassium hydroxide In phosphate buffer; acetone at 27℃;
With sodium hydroxide In methanol; dimethyl sulfoxide at 0 - 25℃; for 12.5h;
With sulfuric acid C.1 COMPARATIVE EXAMPLE 1 COMPARATIVE EXAMPLE 1 100 g of crude methyl cinnamate and 926.8 g of 2.8% caustic soda were placed in a 2-liter flask equipped with a thermometer and a stirrer, and the solution was then stirred at 80° C. for 30 minutes to carry out hydrolysis. An active carbon treatment was omitted. The abovementioned aqueous solution was maintained at 40° C., and 137.1 g of 25% sulfuric acid was added dropwise to precipitate the crystals of cinnamic acid.
With sulfuric acid In toluene C.2 COMPARATIVE EXAMPLE 2 COMPARATIVE EXAMPLE 2 100 g of crude methyl cinnamate and 926.8 g of 2.8% caustic soda were placed in a 2-liter flask equipped with a thermometer and a stirrer, and the solution was then stirred at 80° C. for 30 minutes to carry out hydrolysis. An active carbon treatment was omitted. Then, 100 g of toluene was added to this aqueous solution, followed by stirring at 80° C. for 30 minutes. After the stop of the stirring, the solution was allowed to stand and separate and the resultant toluene layer was then removed. The resultant aqueous layer was placed in a 2-liter flask equipped with a thermometer and a stirrer and then maintained at 40° C., and 137.1 g of 25% sulfuric acid was added dropwise to precipitate the crystals of cinnamic acid.

Reference: [1]Current Patent Assignee: BELROSE PHARMA INC - US2009/17004, 2009, A1
[2]Mata; Mascaretti [Tetrahedron Letters, 1988, vol. 29, # 52, p. 6893 - 6896]
[3]Salomon, Claudio J.; Mata, Ernesto G.; Mascaretti, Oreste A. [Tetrahedron, 1993, vol. 49, # 18, p. 3691 - 3734]
[4]Sharma, Lalima; Nayak, Mrinal K.; Chakraborti, Asit K. [Tetrahedron, 1999, vol. 55, # 31, p. 9595 - 9600]
[5]Barbayianni, Efrosini; Fotakopoulou, Irene; Schmidt, Marlen; Constantinou-Kokotou, Violetta; Bornscheuer, Uwe T.; Kokotos, George [Journal of Organic Chemistry, 2005, vol. 70, # 22, p. 8730 - 8733]
[6]Rohand, Taoufik; Tanemura, Kiyoshi [Tetrahedron Letters, 2020, vol. 61, # 44]
[7]Metternich, Jan B.; Gilmour, Ryan [Journal of the American Chemical Society, 2016, vol. 138, # 3, p. 1040 - 1045]
[8]Nayak, Mrinal K.; Chakraborti, Asit K. [Chemistry Letters, 1998, # 4, p. 297 - 298]
[9]Chakraborti, Asit K.; Sharma, Lalima; Nayak, Mrinal K. [Journal of Organic Chemistry, 2002, vol. 67, # 8, p. 2541 - 2547]
[10]Cativiela, Carlos; Figueras, Francois; Fraile, Jose M.; Garcia, Jose I.; Mayoral, Jose A. [Tetrahedron Letters, 1995, vol. 36, # 23, p. 4125 - 4128]
[11]Sidorenko, T.N.; Terent'eva, G.A.; Raida, V.S.; Andrienko, O.S.; Savinykh, Yu.V.; Aksenov, V.S. [Chemistry of Heterocyclic Compounds, 1982, vol. 18, # 12, p. 1246 - 1250][Khimiya Geterotsiklicheskikh Soedinenii, 1982, vol. 18, # 12, p. 1618 - 1622]
[12]Basak, Amit; Bhattacharya, Gautam; Palit, Sunanda K. [Bulletin of the Chemical Society of Japan, 1997, vol. 70, # 10, p. 2509 - 2513]
[13]Garnelis, Thomas; Athanassopoulos, Constantinos M.; Papaioannou, Dionissios; Eggleston, Ian M.; Fairlamb, Alan H. [Chemistry Letters, 2005, vol. 34, # 2, p. 264 - 265]
[14]Current Patent Assignee: MITSUI CHEMICALS,INC. - US5206430, 1993, A
[15]Current Patent Assignee: MITSUI CHEMICALS,INC. - US5206430, 1993, A
  • 9
  • [ 103-26-4 ]
  • [ 29900-75-2 ]
YieldReaction ConditionsOperation in experiment
91% With hydroxylamine; 1,8-diazabicyclo[5.4.0]undec-7-ene In methanol; water at 20℃; for 0.5h; Preparation of (E)-N-Hydroxy-3-phenyl-acrylamide (Table 2, entry 15) 1,8-Diazabicyclo[5.4.0]undec-7-ene (0.28 ml, 1.85 mmol, 3.0 eq) wasadded to a solution of (E)-3-Phenyl-acrylic acid methyl ester (100 mg, 0.62mmol, 1.0 eq) in methanol (0.35 mL). The resulting solution was stirred at roomtemperature and hydroxylamine in aqueous solution 50% (0.38 ml, 6.17 mmol, 10.0eq) was added. After 30 minutes the reaction was stopped and purified bypreparative HPLC to afford (E)-N-Hydroxy-3-phenyl-acrylamide(92 mg, 0.56 mmol, 91%) as an off-whitesolid: MS ES+ m/z 164.35(M+H)+; 1H NMR (400 MHz, DMSO-d6) δ 10.67 (s, 1H), 7.56 (d, J = 7.2 Hz, 2H), 7.48(d, J = 15.8 Hz, 1H), 7.44 - 7.30 (m, 3H), 6.51 (d, J = 15.8 Hz,1H) ; 13C NMR (101 MHz, DMSO-d6) δ 163.0, 138.6, 135.0, 129.7, 129.1, 127.7, 119.
65% With potassium hydroxide; hydroxylamine hydrochloride In methanol at 20℃; for 36h;
61% With potassium hydroxide; hydroxylamine hydrochloride In methanol 1.) -5 deg C, 5 h, 2.) room temp., 5 d;
With potassium hydroxide; hydroxylamine hydrochloride In methanol
35 g With hydroxylamine hydrochloride; potassium hydroxide In methanol at 0 - 20℃; for 3h; The preparation method of compound 1 in this application (in the above general formula I, R1 is H, R2 is H): 34.1g hydroxylamine hydrochloride is dissolved in 500ml methanol,Cool down to 0,Add 52 g of potassium hydroxide to the methanol solution of hydroxylamine hydrochloride in batches at 0°C,After the addition, continue to stir for 15 min at 0°C,Add 50g methyl cinnamate to the mixture,Warm up to room temperature and react for 3h,The raw material reaction is complete.Point the plate (developing agent: petroleum ether: ethyl acetate = 3:1). Filter to remove potassium chloride, concentrate the filtrate to dryness, add 40ml of water to dissolve it, add 1:1 hydrochloric acid to adjust pH=7, filter, continue to add 1:1 hydrochloric acid to acidify the solid to pH=1, filter, and dry at 65°C to obtain 35g product.

  • 10
  • [ 103-26-4 ]
  • [ 81691-59-0 ]
YieldReaction ConditionsOperation in experiment
85% With water; 4-methylmorpholine N-oxide In acetone at 20℃;
84% With sodium periodate; sulfuric acid In water; ethyl acetate; acetonitrile at 0℃; for 0.0333333h;
84% With ruthenium trichloride; sodium periodate; sulfuric acid In ethyl acetate; acetonitrile at 0℃; for 0.0833333h;
83% With 4-methyl-morpholine; carbon dioxide; dihydrogen peroxide In water; acetone at 25℃;
82% With sodium periodate; cerium(III) chloride In water; ethyl acetate; acetonitrile at 0℃; for 0.0833333h;
82% With magnesium(II) perchlorate hexahydrate; Fe<SUP>II</SUP>(OTf)<SUB>2</SUB>(tris((5-(triisopropylsilyl)pyridin-2-yl)methyl)amine); dihydrogen peroxide In water; acetonitrile at 20℃; for 1h; chemoselective reaction;
81% With potassium osmate(VI) dihydrate; water; 4-methylmorpholine N-oxide In acetone; acetonitrile at 20℃; for 16h;
49% With 4-methylmorpholine N-oxide In water; acetone at 100℃; for 3h; General procedure for the dihydroxylation of alkenes General procedure: alkenesTo a stirred solution of alkene (1, 1 mmol) in a mixture ofacetone:H2O 2:1 (3 mL) in a pressure tube, OsO2-Fe3O4(10 mg,0.08% of osmium) and NMO (234 mg, 2 mmol) were added. Theresulting mixture was stirred at 100C during 3 h. The catalyst wasremoved by a magnet and the resulting solution was extracted withether. The organic phases were dried over MgSO4, and the solventswere removed under reduced pressure. The product was usuallypurified by chromatography on silica gel (hexane/ethyl acetate)to give the corresponding products 2 or 4. Physical and spectro-scopic data as well as literature for all compounds are includedas Appendices A and B. FT-IR spectra were obtained on a Nicoletimpact 400D spectrophotometer. NMR spectra were recorded ona Bruker AC-300 apparatus (300 MHz for1H and 75 MHz for13C)using CDCl3as a solvent and TMS as internal standard for1H and13C; chemical shifts are given in (parts per million) and couplingconstants (J) in Hertz. Mass spectra (EI) were obtained at 70 eVon a spectrometer Agilent GC/MS-5973N, giving fragment ions inm/z with relative intensities (%) in parentheses. Thin layer chro-matography (TLC) was carried out on DC-Fertigfolien ALUGRAMplates coated with a 0.2 mm layer of silica gel; detection by UV254light, staining with phosphomolybdic acid [25 g phosphomolybdicacid, 10 g Ce(SO4)2·4H2O, 60 mL of concentrated H2SO4and 940 mLH2O]. Column chromatography was performed using silica gel 60of 35-70 mesh.
With pyridine; osmium(VIII) oxide
With osmium(VIII) oxide; sodium hydrogensulfite In toluene at -78℃; Yield given;
52 mg With sodium periodate; cerium(III) chloride In ethyl acetate; acetonitrile at 0℃;
55 %Spectr. With TM1459 cupin superfamily protein from Thermotoga maritima, mer-His52,54,58,92-complex with cis-aqua(hydroxo)osmium(III); dihydrogen peroxide In <i>tert</i>-butyl alcohol at 70℃; for 5h; stereoselective reaction;

Reference: [1]Ley, Steven V.; Ramarao, Chandrashekar; Lee, Ai-Lan; stergaard, Niels; Smith, Stephen C.; Shirley, Ian M. [Organic Letters, 2003, vol. 5, # 2, p. 185 - 187]
[2]Plietker, Bernd; Niggemann, Meike [Organic Letters, 2003, vol. 5, # 18, p. 3353 - 3356]
[3]Plietker, Bernd; Niggemann, Meike; Pollrich, Anja [Organic and Biomolecular Chemistry, 2004, vol. 2, # 8, p. 1116 - 1124]
[4]Balagam, Bharathi; Mitra, Ranjan; Richardson, David E. [Tetrahedron Letters, 2008, vol. 49, # 6, p. 1071 - 1075]
[5]Plietker, Bernd; Niggemann, Meike [Journal of Organic Chemistry, 2005, vol. 70, # 6, p. 2402 - 2405]
[6]Borrell, Margarida; Costas, Miquel [Journal of the American Chemical Society, 2017, vol. 139, # 36, p. 12821 - 12829]
[7]Bengtsson, Christoffer; Nelander, Hanna; Almqvist, Fredrik [Chemistry - A European Journal, 2013, vol. 19, # 30, p. 9916 - 9922]
[8]Cano, Rafael; Pérez, Juana M.; Ramón, Diego J. [Applied Catalysis A: General, 2014, vol. 470, p. 177 - 182]
[9]Cooper,R. et al. [Israel Journal of Chemistry, 1977, vol. 16, p. 12 - 15]
[10]Fuji, Kaoru; Tanaka, Kiyoshi; Miyamoto, Hisashi [Tetrahedron Letters, 1992, vol. 33, # 28, p. 4021 - 4024]
[11]Scholte, Andrew A.; Mi, Hyun An; Snapper, Marc L. [Organic Letters, 2006, vol. 8, # 21, p. 4759 - 4762]
[12]Fujieda, Nobutaka; Nakano, Takumi; Taniguchi, Yuki; Ichihashi, Haruna; Sugimoto, Hideki; Morimoto, Yuma; Nishikawa, Yosuke; Kurisu, Genji; Itoh, Shinobu [Journal of the American Chemical Society, 2017, vol. 139, # 14, p. 5149 - 5155]
  • 11
  • [ 103-26-4 ]
  • rac-(R,S)-methyl 2,3-dibromo-3-phenylpropanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With hydrogen bromide; dihydrogen peroxide In tetrachloromethane at 20℃; for 2h;
97% With Oxone; ammonium bromide In water; acetonitrile for 12h; Reflux; stereoselective reaction; General procedure for the synthesis of dibromides: General procedure: To a solution of olefin (2 mmol) in CH3CN (10 mL) were added NH4Br (4.4 mmol) and Oxone (2.2 mmol) and the mixture was stirred at reflux temperature for the time shown in Table 2. After completion (as indicated by TLC), the reaction mixture was filtered and the solvent evaporated under reduced pressure. The products were purified by column chromatography (Hexane/EtOAc, 98:2) over silica gel.
89% With Selectfluor; potassium bromide In water; acetonitrile for 2h;
(bromination);
With bromine In dichloromethane for 1h; Heating;
With bromine In chloroform at 20℃;
With bromine

  • 12
  • [ 103-26-4 ]
  • [ 122743-18-4 ]
YieldReaction ConditionsOperation in experiment
100% With hydroquinidine 1,4-phthalazinediyl diether In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 20℃; for 10h;
99% With AD-mix-α
92% With osmium(VIII)-tetroxide; dihydroquinidine 9-O-(4-chlorobenzoate); potassium hexacyanoferrate(III)
92% With AD-mix-α; potassium carbonate; potassium hexacyanoferrate(III) In <i>tert</i>-butyl alcohol at 20℃; for 3.5h;
92% With Resin-OsO4; hydroquinidine 1,4-phthalazinediyl diether; potassium hexacyanoferrate(III) In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 20℃;
89% With methanesulfonamide; AD-mix α In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 0 - 25℃; for 22h; Inert atmosphere;
87% With potassium dioxotetrahydroxoosmate(VI); (DHQ)2-PHAL; potassium hexacyanoferrate(III) In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 20℃;
85% With methanesulfonamide; AD-mix α; lithium hydroxide monohydrate In <i>tert</i>-butyl alcohol at 20℃; for 18h;
83% With osmium(VIII)-tetroxide; polymeric cinchona alkaloid containing 1,4-bis(9-O-quininyl)phthalazine and methyl methacrylate; lithium hydroxide monohydrate; potassium carbonate; potassium hexacyanoferrate(III) In <i>tert</i>-butyl alcohol at 10℃; for 20h;
83% With osmium(VIII)-tetroxide; 1-methyl-1,3-dihydro-indol-2-one; AD-mix-α In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 20℃; for 24h;
77% With methanesulfonamide; (DHQ)<SUB>2</SUB>PHAL In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 25℃; for 24h; Inert atmosphere; 1.1; 2.1 1) methyl cinnamate C and AD-mix-alph substitution reaction, obtain adjacent diol compound D: 3.65g (22.5mmol, 1eq) methyl cinnamate was dissolved in 110mL tert-butanol and 110mL water, then 31g AD-mix-alpha and 2.15g (22.5mmol, 1eq) methylsulfonamide were added, under nitrogen protection, under the condition of 25 °C stir the reaction for 24 hours; after the reaction was completed, sodium bisulfite solution was added to the obtained system to quench the reaction, and the reaction was extracted three times with ethyl acetate. The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography (PE:EA=2:1) to obtain the product as a white solid with a yield of 77%.
76% With methanesulfonamide; K2<OsO2(OH)4>; potassium carbonate; potassium hexacyanoferrate(III)
72% With osmium(VIII)-tetroxide; AD-mix-α; potassium carbonate; potassium hexacyanoferrate(III) In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol for 18h; Ambient temperature;
72% With (3a,9R,3'''a,4'"b,9'"R)-9,9'-[1,4-phthalazinediylbis(oxy)]bis[6'-(methyloxy)-10,11-dihydrocinchonan]; osmium(VIII)-tetroxide; N-Methylmorpholine N-oxide In lithium hydroxide monohydrate; propan-2-one at 10℃; for 48h;
71% With 1-methyl-1,3-dihydro-indol-2-one; AD-mix-α; potassium dioxotetrahydroxoosmate(VI) In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol for 23h; Ambient temperature;
70%
70% With K<SUB>2</SUB>OsO<SUB>4</SUB>.2H<SUB>2</SUB>O; N-Methylmorpholine N-oxide; hydroquinidine 1,4-phthalazinediyl diether; <i>tert</i>-butyl alcohol at 23 - 40℃; for 2h; Large scale; enantioselective reaction;
66% With AD-mix-α; methanesulfonamide In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 23℃; for 24h;
With methanesulfonamide; hydroquinidine 1,4-phthalazinediyl diether In lithium hydroxide monohydrate; <i>tert</i>-butyl alcohol at 0 - 25℃; for 22h; Inert atmosphere;

Reference: [1]Schmidt, Bernd [Journal of Organic Chemistry, 2004, vol. 69, # 22, p. 7672 - 7687]
[2]Bourghida, Ahmed; Wiatz, Vincent; Wills, Martin [Tetrahedron Letters, 2001, vol. 42, # 49, p. 8689 - 8692]
[3]Zhou, Wei-Shan; Yang, Zhi-Cai [Tetrahedron Letters, 1993, vol. 34, # 44, p. 7075 - 7076]
[4]Kim, Kwang Jin; Choi, Han Young; Hwang, Soon Ho; Park, Yil Sung; Kwueon, Eun Kyung; Choi, Doo Seong; Song, Choong Eui [Chemical Communications, 2005, # 26, p. 3337 - 3339]
[5]Choudary, Boyapati M.; Chowdari, Naidu S.; Jyothi, Karangula; Kantam, Mannepalli L. [Journal of the American Chemical Society, 2002, vol. 124, # 19, p. 5341 - 5349]
[6]Hüttel, Stephan; Testolin, Giambattista; Herrmann, Jennifer; Planke, Therese; Gille, Franziska; Moreno, Maria; Stadler, Marc; Brönstrup, Mark; Kirschning, Andreas; Müller, Rolf [Angewandte Chemie - International Edition, 2017, vol. 56, # 41, p. 12760 - 12764][Angew. Chem., 2017, vol. 129, # 41, p. 12934 - 12938]
[7]Palomo, Claudio; Oiarbide, Mikel; Landa, Aitor [Journal of Organic Chemistry, 2000, vol. 65, # 1, p. 41 - 46]
[8]Bengtsson, Christoffer; Nelander, Hanna; Almqvist, Fredrik [Chemistry - A European Journal, 2013, vol. 19, # 30, p. 9916 - 9922]
[9]Song, Choong Eui; Yang, Jung Woon; Ha, Hyun Joon; Lee, Sang-Gi [Tetrahedron Asymmetry, 1996, vol. 7, # 3, p. 645 - 648]
[10]Siddiqui, Shafi A.; Srinivasan, Kumar V. [Tetrahedron Asymmetry, 2007, vol. 18, # 17, p. 2099 - 2103]
[11]Current Patent Assignee: BEIJING DYNE INST OF CHILDREN MEDICINE; SHANDONG DYNE MARINE ORGANISM PHARMACY - CN114106034, 2022, A Location in patent: Paragraph 0086-0089; 0103-0104
[12]Nicolaou, Kyriacos Costa; Dai, Wei-Min; Guy, Rodney Kiplin [Angewandte Chemie, 1994, vol. 106, # 1, p. 38 - 69]
[13]Harada, Naoyuki; Hashiyama, Tomiki; Ozaki, Kunihiko; Yamaguchi, Tetsuo; Ando, Akira; Tsujihara, Kenji [Heterocycles, 1997, vol. 44, # 1, p. 305 - 318]
[14]Song, Choong Eui; Oh, Chun Rim; Roh, Eun Joo; Choi, Jung Hoon [Tetrahedron Asymmetry, 2001, vol. 12, # 11, p. 1533 - 1535]
[15]Wang; Kolb; Sharpless [Journal of Organic Chemistry, 1994, vol. 59, # 17, p. 5104 - 5105]
[16]Mandai, Tadakatsu; Okumoto, Hiroshi; Oshitari, Tetsuta; Nakanishi, Katsuyoshi; Mikuni, Katsuhiko; Hara, Ko-ji; Hara, Ko-zo; Iwatani, Wakao; Amano, Tetsuya; Nakamura, Kosho; Tsuchiya, Yoshinori [Heterocycles, 2001, vol. 54, # 2, p. 561 - 566]
[17]Lu, Xinbo; Xu, Zhunle; Yang, Guojun [Organic Process Research and Development, 2000, vol. 4, # 6, p. 575 - 576]
[18]Yamada, Ken; Kurokawa, Toshiki; Tokuyama, Hidetoshi; Fukuyama, Tohru [Journal of the American Chemical Society, 2003, vol. 125, # 22, p. 6630 - 6631]
[19]Planke, Therese; Moreno, María; Hüttel, Stephan; Fohrer, Jörg; Gille, Franziska; Norris, Matthew D.; Siebke, Maik; Wang, Liangliang; Müller, Rolf; Kirschning, Andreas [Organic Letters, 2019, vol. 21, # 5, p. 1359 - 1363]
  • 13
  • [ 100-52-7 ]
  • [ 96-32-2 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
88% With tributylstibine at 100℃; for 6h;
88% With tributylstibine at 110℃; for 6h;
87% With tri-n-butylarsine; cadmium at 100℃; for 20h;
86% With triphenyl phosphite; tri-n-butylarsine; potassium carbonate In tetrahydrofuran; acetonitrile for 30h; Ambient temperature;
86% With triphenyl phosphite; tri-n-butylarsine; potassium carbonate In tetrahydrofuran; acetonitrile for 30h; Ambient temperature; other aldehydes, reaction with ω-bromoacetophenone, var. reaction times;
81% With tri-n-butylarsine; zinc In neat (no solvent) at 80℃; for 12h;
75% With 1-phenylarsolane; N-ethyl-N,N-diisopropylamine; HSiPh3 In toluene at 100℃; for 24h; Schlenk technique; Inert atmosphere;
74% With diphenylsilane; sodium carbonate; 3-methyl-1-phenyl-2,3,4,5-tetrahydro-1H-phosphole-1-oxide In toluene at 100℃; for 24h; Inert atmosphere; stereoselective reaction;
74% With diphenylsilane; sodium carbonate In toluene at 100℃; for 24h; Inert atmosphere; Sealed tube; 8 Preparation of Compounds 2-19.; The general procedure is outlined at the top of Figure 6.; In air, a 1-dram vial equipped with a stir-bar was charged with 3- methyl-l-phenylphospholane-1 -oxide (1) (19 mg, 10 mol %) and base (1.5 mmol, 1.5 equiv.); if the aldehyde was solid, it was added at this point (1.0 mmol, 1.0 equiv,). The vial was then sealed with a septum and purged with argon. Distilled solvent (0.33 mL), silane (1.1-1.5 mmol, 1.1-1.5 equiv.), and organohalide (1.1-1.5 mmol, 1.1 -1.5 equiv.) were added; and if the aldehyde was liquid, it was added at this point (1.0 mmol, 1.0 equiv.). The septum was replaced with a PTFE-lined screw cap under an inert atmosphere, and the reaction was heated at 1000C for 24 h. When GC/MS analysis was not performed, the crude reaction mixture was filtered tlnough a plug of celite, concentrated in vacuo, and purified via flash column chromatography. It is important that the reactions are stirred vigorously in order to achieve maximum yield.GC/MS Analysis Conditions: Following the General Procedure, /7-undecane (GC/MS internal standard, 100 μL/mmol aldehyde) was injected via syringe. The reaction mixture was passed through a short pad of silica gel and analyzed by a GC/MS/MS Varian 240.; (E) -Methyl china mate (2) was obtained from the reaction of benzaldehyde (100 μL, 1.0 mmo, 1.0 equiv.), methyl bromoacetate (114 μL, 1.2 mmol, 1.2 equiv.), diphenylsilaiie (200 μL, 1.1 mniol, 1.1 equiv.) and sodium carbonate (159 mg, 1.5 mmol, 1.5 equiv.) in toluene (0.33 mL) at 100°C for 24 h. The crude product was purified via flash column chromatography (benzene/pentane, 50:50, Rf = 0.25) to afford the product as a white solid (120 mg, 74%, E:Z 1 :0), Spectral data match that of commercially available product (Aldrich). When this reaction was performed with methyl chloroacetate, the isolated yield was 68%.
74% With diphenylsilane; sodium carbonate; 3-methyl-1-phenyl-2,3,4,5-tetrahydro-1H-phosphole-1-oxide In toluene at 100℃; for 24h; Inert atmosphere;
66% With ethyloxirane; Tributylphosphine oxide; phenylsilane In 1,4-dioxane at 150℃; for 3h; Microwave irradiation; Inert atmosphere; stereoselective reaction;
54% With trichlorosilane; triethylamine; Triphenylphosphine oxide In dichloromethane at -10 - 20℃;
186 mg With ethyloxirane; Tributylphosphine oxide; phenylsilane In 1,4-dioxane at 150℃; for 3h; Microwave irradiation; Inert atmosphere; diastereoselective reaction;

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  • 14
  • [ 4891-38-7 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
84% With ethanol; palladium diacetate; (R,R)-1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane In acetonitrile at 140℃; for 24h; stereoselective reaction; E-Alkenes; General Procedure General procedure: To a 15 mL pressure tube were added diarylacetylene 1 (0.10 mmol),Pd(OAc)2 (2.24 mg, 0.01 mmol), R,R-DIPAMP (9.16 mg, 0.02 mmol),and then EtOH (291.5 L, 5 mmol) and CH3CN (1.5 mL) were added.The resulting solution was stirred at 140 °C for about 36 h. After completionof the reaction, the solution was cooled to rt and diluted withEtOAc (10 mL). The combined organic phases were washed withbrine, and the aqueous phase was extracted with EtOAc. The organicphase was dried (anhyd Na2SO4), filtered, and concentrated in vacuo.The crude product was purified by column chromatography (n-hexaneor n-hexane/EtOAc 100:1 to 40:1) to afford the desired product
82% With palladium diacetate; (R,R)-1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane In ethanol; acetonitrile at 145℃; for 36h; 17 Methyl phenylpropynoate (0.20 mmol), Pd(OAc) 2 (0.02 mmol, 4.48 mg), R, was added to a 15 ml pressure-resistant tube.R-DIPAMP (0.2 mmol, 18.32 mg), 95% EtOH (10 mmol, 595 L) and CH3CN (1.5 mL), stirring at 145 ° C36 hours.After the reaction was completed, it was cooled to room temperature, and ethyl acetate (10 mL) was added. The organic phase was washed three times with brine, dried over anhydrous Na. The crude product was separated and purified by column chromatography to give trans-phenyl methacrylate as a colorless liquid, 25.2 mg, yield 82%.
76% With di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]diiridium; ethanol; 1,2-(diphenylphosphino)ethane In tetrahydrofuran at 120℃; for 22h; Inert atmosphere; stereoselective reaction;
62% With sodium hydrogen telluride In ethanol Ambient temperature;
35% With formic acid; C44H35ClO4P2Ru; anhydrous sodium formate In 1,2-dimethoxyethane at 90℃; for 1h; Inert atmosphere; Schlenk technique; stereoselective reaction;
8% With hydrogen; Ir(SiMe<SUB>2</SUB>CH<SUB>2</SUB>PPh<SUB>2</SUB>)<SUB>2</SUB>Cl at 20℃; for 20h; stereoselective reaction;
Multi-step reaction with 2 steps 1: 90 percent / quinoline; H2 / Pd-CaCO3 / methanol / 18 h / 20 °C 2: 98 percent / triethylamine; tributyltin hydride / palladium(II) acetate / CH2Cl2 / 8 h / Heating
Multi-step reaction with 2 steps 1: tributylphosphine / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere 2: methanol

  • 15
  • [ 591-50-4 ]
  • [ 292638-85-8 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
100% In 1-methyl-pyrrolidin-2-one at 100℃; for 120h;
100% With palladium diacetate; 15-crown-15 tagged triarylphoshine; triethylamine In tetrahydrofuran for 8h; Heating;
100% With triethylamine In 1,4-dioxane at 100℃; for 1h;
100% With triethylamine; N-benzyl-2-(2-bromophenyl)-benzimidazole In 1-methyl-pyrrolidin-2-one at 116℃; for 16h;
100% With triethylamine In N,N-dimethyl acetamide at 80℃; for 0.333333h;
100% With triethylamine In acetonitrile at 100℃; for 12h;
100% With triethylamine In N,N-dimethyl-formamide at 140℃; for 6h;
100% With anhydrous sodium carbonate In 1-methyl-pyrrolidin-2-one at 140℃; for 14h;
100% With triethylamine In N,N-dimethyl-formamide at 140℃; for 14h;
100% With triethylamine In N,N-dimethyl-formamide at 140℃; for 3h;
100% With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 6h;
100% With triethylamine In N,N-dimethyl acetamide at 90℃; for 9h;
99% With palladium diacetate; molecular sieve; tetra-n-butyl-ammonium chloride; Sodium hydrogenocarbonate; triphenylphosphine In acetonitrile at 60℃; for 3.5h;
99% With palladium diacetate; tetra-n-butyl-ammonium chloride; Sodium hydrogenocarbonate; triphenylphosphine In acetonitrile at 60℃; for 3.5h; influence of tetraalkylammonium salts in Heck-type reaction; different solvent, inorganic bases;
99.9% With triethylamine In 1,4-dioxane at 100℃; for 3h;
99.2% With triethylamine; 3-butyl-5-hydroxymethyl-1-methyl-3H-imidazol-1-ium triflimide at 100℃; for 0.5h;
99% With polystyrene-supported palladacycle catalyst; anhydrous Sodium acetate In N,N-dimethyl acetamide at 100℃; for 8h;
99% With N,N-disubstituted cyclic bis(thiourea); triethylamine In N,N-dimethyl-formamide at 100℃; for 2h;
99% With tributyl-amine In acetonitrile at 90℃; for 5h;
99% With polymeric palladium; triethylamine In N,N-dimethyl-formamide at 120℃; for 2.5h;
99% With anhydrous Sodium acetate In ISOPROPYLAMIDE at 100℃; for 8h; 2 Compound 5 (30 mg, 2 μmol Pd), iodobenzene (0.20 g, 1 mmol), methyl acrylate (0.13 g, 1.5 mmol), sodium acetate (0.12 g, 1.5 mmol), and N,N-dimethylacetamide (3 mL) were sequentially added to a 15 mL septum-sealed test tube under protection of nitrogen. The reaction mixture was heated at 100° C. for 8 h. After it was cooled to the room temperature, 8 mL of anhydrous ether was added to precipitate compound 5. The mixture was centrifuged and the upper liquid layer was transferred via a syringe into a 20 mL round-bottom flask. Repeated the above precipitation procedure once. The combined liquid layer was concentrated under reduced pressure to give an oily residue. A saturated ammonium chloride solution (5 mL) was then added. The resulting mixture was extracted by ethyl acetate (10 mL×3), dried over anhydrous magnesium sulfate, filtrated, and concentrated to give a crude product. The crude product was further purified by column chromatography (silica gel, hexane/ethyl acetate=4/1) to give 0.16 g (99% yield) of trans-methyl cinnamate. Rf=0.53 (9:1 hexane:ethyl acetate), 1H NMR (300 MHz, CDCl3) δ 3.81 (s, 3H), 6.45 (d, J=15.6 Hz, 1H), 7.29-7.64 (m, 5H), 7.69 (d, J=15.6 Hz, 1H) ppm.
99% With triethylamine In lithium hydroxide monohydrate; N,N-dimethyl-formamide; toluene at 100℃; for 20h;
99% With polymer supported (2,3-dimethylimidazolium-1-yl)methyl hydroxide; polymer supported (3-methylimidazolium-1-yl)methyl palladium(0) chloride In N,N-dimethyl-formamide at 130℃; for 2.66667h;
99% With potassium carbonate In 1,4-dioxane at 100℃; for 6h; Heck reaction of iodobenzene with various alkenes A typical optimization study was done by the following procedure. To a 25 mL flask was added the aryl halide, appropriate alkene and base in a mole ratio of 1:1.25:2 respectively. To this were added 5.00 mg of SnPPd and 5 mL of solvent. The reaction mixture was heated to 100 °C with stirring. The reaction was monitored by TLC. At the end of the reaction, dilute hydrochloric acid was added to the reaction mixture to quench the reaction. The product(s) was extracted with diethyl ether solvent (15 mL × 3) and the organic extract was washed with water and then with saturated sodium chloride solution. Magnesium sulfate was added to the ethereal solution to remove the water and ethereal solution was evaporated to give the crude product. This crude product was purified by column chromatography. The purity of the products was checked by proton NMR as well as by melting point measurements.; The results of the Heck coupling experiments are tabulated in Tables S1 and S2.The best optimized conditions as found for the iodobenzene- styrene coupling reaction were used for all coupling reactions involving iodobenzene. These are: potassium carbonate as the base (table S2; entry4) and 1,4-dioxane (table S1 ; entry 1) as the solvent; temperature of the reaction, 100 C .
99% With N,N,N-tributylbutan-1-aminium fluoride; palladium diacetate; potassium carbonate at 70℃; for 18h; air;
99% With potassium hydroxide In N,N-dimethyl-formamide at 80℃; for 10h; Inert atmosphere; Schlenk technique; General procedure for the Heck reaction General procedure: Palladium complex (1 or 2) (1.0 mmol), aryl halide (1.0 mmol), methyl acrylate (1.2 mol), base (4 mmol), and DMF (10 mL) were placed in a 100-ml Schlenk tube, and the reaction mixture was subjected to a freeze-thaw cycle before being heated at 80 °C for 10 h. Completion of the reaction was monitored in situ by use of gas chromatography after a specific time. After complete conversion, the reaction mixture was cooled and extracted with ethyl acetate-hexane. The extract was filtered through a pad of silica gel with copious washing, concentrated, and purifiedby flash chromatography on silica gel. Product purity was checked by NMR spectroscopy.
99% With anhydrous sodium carbonate In N,N-dimethyl-formamide at 100℃; for 12h; 3.2.5. General procedure for heck reaction General procedure: A round bottom flask was charged with aryl halide (15 mmol), olefins such as methyl and methyl methacrylate and acrylonitrile (15 mmol) using DMF as a solvent (100 mL), Then Na2CO3 as base (15 mmol) and catalyst (0.5 mol %) were added. The stirring solution was refluxed at 100°C for 12 h. After requisite time, the reaction mixture was cooled to room temperature. The palladium catalyst was separated from the mixture by filtration. The solution diluted with water (30 mL) and product extracted with ethyl acetate (3×10 mL). Then, the product was concentrated under reduced pressure. This product was purified and crystallized with ethanol and water (1:1).
99% With tripotassium phosphate tribasic; C21H15N3O3Pd In lithium hydroxide monohydrate at 130℃; for 4h; Sealed tube;
98% With RhCl((C6H5)3P)3; potassium carbonate In various solvent(s) at 110℃; for 24h;
98% With palladium diacetate; N,N,N-tributyl-1-butanaminium iodide In various solvent(s) at 60℃; for 1h;
98.7% With 3C12H24KO6*O4P(3-); potassium carbonate; palladium (II) chloride In lithium hydroxide monohydrate; N,N-dimethyl-formamide at 110℃; for 1h;
98% With palladium diacetate; triethylamine at 60℃; for 2h;
98% With C28H24Cl2N4Pd2; triethylamine In N,N-dimethyl-formamide at 80℃; for 8h; Schlenk technique; Catalytic experiments General procedure: A dry 100 ml capacity Schlenk tube equipped with a magnetic bar was charged with iodobenzene (10 mmol), methyl acrylate or butyl acrylate (11 mmol) and triethylamine (10 ml). The catalyst (0.01 mmol) was dissolved in 10 ml DMF and it was then transferred quantitatively to the reaction vessel. The reaction was heated under stirring at 80 °C. Samples were drawn at regular intervals and analyzed by GC to determine the percentage conversions. The coupling product was isolated by pouring the reaction mixture in water (50 ml) and extracted with CH2Cl2 to give a pure product which was confirmed by 1H NMR spectroscopy. Mercury drop experiments were performed in duplicate by adding two drops of elemental mercury to the reaction described above and the product was also confirmed by 1H NMR spectroscopy.
98% With triethylamine In neat (no solvent) at 20℃; for 0.25h; Green chemistry; diastereoselective reaction; Typical Procedure for the Mizoroki-Heck Cross-Coupling Reaction General procedure: FMMWCNTs(at)CPA(at)SMTU(at)PdII NPs (IV) (0.35 mol-%,0.015 g) were added to a mixture of triethylamine (NEt3) (2 mmol, 0.202 g), methyl acrylate (1.2 mmol, 0.108 mL), and iodobenzene (1.0 mmol, 0.203 g) in solvent-free conditions at room temperature. After the completion of the reaction (15 min)which was monitored by TLC, the nanocatalyst was separated by a magnetic field, washed with ethyl acetate, and dried at room temperature for 24 h to be used in the next run. The reaction mixture was then extracted with ethyl acetate (55 mL) and the combined organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the crude product was purifiedby TLC (or column chromatography using n-hexane/ethylacetate (50 : 1)) using n-hexane/ethyl acetate (8 : 2) to produce the pure methyl cinnamate (0.153 g, 98% yield).
98% With ethylene glycol; triethylamine In N,N-dimethyl acetamide at 110℃; for 10h; 2.5 Typical procedure for heck reaction General procedure: Aromatic iodide (1.0mmol), alkene (2.0mmol), triethylamine (2.5mmol) and glycol (0.2g) were added into a tubular reactor containing 25mgPdACPVC fiber mat (Pd content: 2.21μmol) and 3.2mLN,N-dimethylacetamide (DMAc). The reaction mixture was carried out with magnetically stirring at 110°C. The reaction progress was monitored by thin layer chromatography (TLC) and gas chromatograph/mass spectrometer (GC/MS). After reaction, 10mL water was added into the reaction mixture to quench the reaction and then the reaction mixture was extracted with ethyl acetate (3×10mL). Solvent of extracted solution was removed under reduced pressure to afford the crude product, which was further purified by silica gel chromatography. The coupling products were confirmed by 1H NMR spectra and mass spectra.
98% With triethylamine In dimethyl sulfoxide at 100℃; for 0.5h;
98% With triethylamine In N,N-dimethyl-formamide at 100℃; for 3h; Green chemistry; General experimental procedures for Heck reaction General procedure: The reactions were conducted in similar way as for Sonogashira reaction. Stirring the mixture of aryl halide (1.00 mmol), styrene derivative (1.50 mmol), Pd(at)MOF-808 (3 mol %), Et3N (2.00 mmol) and DMF (5.00 mL) at 100 °C for 2-8 h. After cooling down the mixture to room temperature, evaporating the solution under reduced pressure. After that, purifying the residue by silica gel column chromatography to collect the target coupling products
97% With triethylamine In N,N-dimethyl acetamide at 130℃; for 2h;
97% With palladium diacetate; potassium carbonate; 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride In N,N-dimethyl-formamide at 80℃; Sealed tube; 2.2 General procedure for the Heck reactions General procedure: All Heck reactions were carried out in air. A mixture of aryl halide (1.0 mmol), olefins (1.2 mmol), K2CO3 (2 mmol), Pd(OAc)2 (0.5 mol%), and imidazolium salt L2 (1.0 mol%) in DMF (3 mL) was allowed to react in a sealed tube at 80 °C. The reaction mixtures was added to brine (15 mL) and extracted three times with diethyl ether (3 × 15 mL). The further purification of the product was achieved by flash chromatography on a silica gel column using hexane/ethyl acetate (5/1).
97% With anhydrous Sodium acetate In N,N-dimethyl acetamide at 120℃; for 10h; Inert atmosphere; Typical Heck Reaction General procedure: Iodobenzene (0.2 mmol), methyl acrylate (0.3 mmol), sodium acetate (0.3 mmol), Pd/La2O3 (1 mol%), and DMA 2 mL were added to a 25 mL flask equipped with a magnetic stirring bar under nitrogen atmosphere. The reaction mixture was stirred at 120 °C for 10 h. After the reaction, the reaction mixture was cooled to room temperature, separated, and purified by column chromatography (SiO2, ethyl acetate/hexane).Unless otherwise stated, product yields from the Heck reaction were determined by column chromatography. The product was dried under vacuum, weighted, and characterized by NMR spectroscopy.
97% With D-glucose; palladium diacetate; triethylamine In lithium hydroxide monohydrate; acetonitrile at 100℃; for 16h; Sealed tube;
97% With tripotassium phosphate tribasic In N,N-dimethyl-formamide at 140℃; for 2h; 4.5 General procedure for Mizoroki-Heck coupling reactions General procedure: In a 10-mL round-bottomed flask, a mixture of aryl iodide (1mmol), methyl acrylate (1.2mmol), and base (1.2mmol), was placed in 4ml of DMF, then a solution of complex 3a (0.05% mol) in 1mL of DMF was added. The reaction mixture was refluxed for the time stated in Tables1 and 2 at 140°C. The reaction mixture was poured into water (20mL) and extracted with ether or hexane (2×30mL). The combined organic layers were dried over anhydrous sodium sulfate. After the removal of the solvent in vacuo, the resulting crude was purified by column chromatography on silica gel (hexane-ethyl acetate) to give (E)-methyl p-methyl cinnamate (The purified product was identified by means of determination of mp and by 1H and 13C NMR, the data obtained are consistent with literature) [33].
97% With triethylamine In N,N-dimethyl-formamide at 100℃; for 1.5h; Sealed tube;
96% With tributyl-amine at 100℃; for 2h;
96% With triethylamine In acetonitrile for 24h; Heating;
96% With trifuran-2-yl-phosphane; N-ethyl-N,N-diisopropylamine In carbon dioxide at 80℃; for 17h;
96% With trifuran-2-yl-phosphane; N-ethyl-N,N-diisopropylamine In carbon dioxide at 80℃; for 17h; effect of various catalysts, ligands, base, amount of catalyst;
96% With triethylamine In N,N-dimethyl-formamide at 75℃; for 24h;
96% With (3aS,7aS)-1,3-di-o-tolyl-octahydro-benzoimidazole-2-thione; triethylamine In N,N-dimethyl-formamide at 80℃; for 5h;
96% With triethylamine In 1-methyl-pyrrolidin-2-one at 120℃; for 0.416667h;

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[34]Ghasemzadeh, Maryam Sadat; Akhlaghinia, Batool [Australian Journal of Chemistry, 2019, vol. 72, # 9, p. 674 - 692]
[35]Du, Yijun; Qi, Chenze; Qin, Min; Shao, Linjun; Tao, Hongyu; Wang, Qingqing [Journal of Physics and Chemistry of Solids, 2020, vol. 147]
[36]Aryanasab, Fezzeh; Shabanian, Meisam; Laoutid, Fouad; Vahabi, Henri [Applied Organometallic Chemistry, 2021, vol. 35, # 5]
[37]Zhao, Zesheng; Wang, Jie; Zhang, Xiaoli; Lin, Taofeng; Ren, Jianwei; Pang, Wan [Tetrahedron Letters, 2022, vol. 100]
[38]Xiong, Zhengchang; Wang, Nengdong; Dai, Mingji; Li, Ang; Chen, Jiahua; Yang, Zhen [Organic Letters, 2004, vol. 6, # 19, p. 3337 - 3340]
[39]Amini, Mojtaba; Bagherzadeh, Mojtaba; Rostamnia, Sadegh [Chinese Chemical Letters, 2013, vol. 24, # 5, p. 433 - 436]
[40]Li, Zhao-Hao; Xue, Li-Ping; Shang, Pan-Pan; Zhao, Bang-Tun [Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2013, vol. 43, # 10, p. 1476 - 1479]
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  • 16
  • [ 292638-85-8 ]
  • [ 62-53-3 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
79% With tert.-butylnitrite; methanesulfonic acid; palladium diacetate In methanol; N,N-dimethyl-formamide at 25℃; Flow reactor;
77% Stage #1: aniline With tert.-butylnitrite; boron trifluoride diethyl etherate at -15 - 5℃; for 0.583333h; Stage #2: acrylic acid methyl ester With (R,R)-N,N'-(2-MeC6H4)2-N,N'-(cyclohexane-1,2-diyl)thiourea In methanol at 20℃; for 4h;
11% With palladium diacetate; acetic acid In 1,4-dioxane for 8h; Heating;
66 % Chromat. In acetic acid for 5h; Heating;

  • 17
  • [ 292638-85-8 ]
  • [ 98-80-6 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
99% With palladium diacetate; acetic anhydride; 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetic acid at 90℃; for 27h;
96% With potassium fluoride; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; bis(acetylacetonato)palladium(II); propionic acid at 20℃; for 2h; Inert atmosphere; diastereoselective reaction;
90% In water; toluene at 100℃; for 10h;
90% With C48H40N4O4Pd2(4+); trifluoroacetic acid; p-benzoquinone In water at 20℃; for 12h; Inert atmosphere;
82% With trifluoroacetic acid In acetone at 70℃; for 20h;
78% With triphenylphosphine In water; toluene at 100℃; for 20h;
78% With potassium carbonate; triphenylphosphine In water; toluene at 120℃; for 5h; Heating;
75% With manganese(II) acetate In N,N-dimethyl-formamide at 110℃; for 12h;
8% With diisopropylamine; p-benzoquinone In toluene at 80℃; for 1.5h;
73 % Chromat. With palladium diacetate; sodium acetate In acetic acid at 25℃; for 20h;
With [bmpy]2[Pd2Cl6]; oxygen In N,N-dimethyl-formamide at 130℃; for 4h; Schlenk technique; Typical procedure for the oxidative Heck reaction General procedure: The oxidative Heck reaction was carried out in a 50 mL Schlenk tube. The solid substrates: phenylboronic acid (1.5 mmol, 0.184 g) and palladium complex (0.02 mmol) were weighted and placed in the Schlenk tube which was evacuated and filled with oxygen. Next,olefin (1 mmol) and 5 mL of the solvent saturated with oxygen (30 min) were added with a pipette in the atmosphere of oxy-gen. The reactor was closed with a rubber plug and the reaction mixture was stirred in 130°C. After the given reaction time, the reactor was cooled down and the organic products were extracted with 20 mL of diethyl ether. For better phase separation 1 mL of water was added; 0.15 mL of mesitylene was added as an internal standard. The organic products were analyzed using the GC-MS method.

  • 18
  • [ 103-26-4 ]
  • Methyl (2RS,3RS)-2,3-dihydroxy-3-phenylpropionate [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With 4-methylmorpholine N-oxide In water; acetone; acetonitrile at 20℃;
91% With Quinuclidine; potassium osmate(VI); disodium hydrogenphosphate; dipotassium peroxodisulfate; methanesulfonamide; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 20℃; General procedure for racemic dihydroxylation of olefins General procedure: Water (5 mL/mmol substrate) was added to a solid mixture of K2S2O8 (1.5 equiv), Na2HPO4 (3 or 4 equiv), K3Fe(CN)6 (0.2 equiv) or NaIO4 (0.2 equiv), MeSO2NH2 (1 equiv) and K2OsO2(OH)4 (0.05 equiv) at room temperature, and the mixture was stirred for 5 min. Quinuclidine (0.3 equiv), tert-BuOH (5 mL/mmol substrate), and the olefin (1 equiv) were then added sequentially, and the reaction was stirred at room temperature until the olefin was consumed as judged by TLC. A solution of saturated aqueous Na2S2O3 was added, and the mixture was extracted with CH2Cl2 (3 x 5 mL/mmol substrate).The combined organic extracts were dried (Na2SO4), filtered, and concentrated under reduced pressure, and the crude product was purified by flash chromatography to provide the pure diol.
(i) PhCO2Ag, I2, benzene, (ii) Ba(OMe)2, MeOH, CHCl3; Multistep reaction;
Multi-step reaction with 2 steps 1.1: dibromoamine-T / acetonitrile; water / 0.5 h / 20 °C 1.2: 20 °C 2.1: sulfuric acid / water / 20 °C

  • 19
  • [ 103-26-4 ]
  • [ 143505-39-9 ]
YieldReaction ConditionsOperation in experiment
96% With 4-methylmorpholine N-oxide In water; acetone; acetonitrile at 20℃;
96% With N-methyl-2-indolinone; water In acetone; acetonitrile at 20℃; for 20h;
75% With potassium osmate(VI); methanesulfonamide; chiral (DHQD)2PYDZ; water; potassium carbonate; potassium hexacyanoferrate(III) In <i>tert</i>-butyl alcohol at 0℃; for 96h;
  • 20
  • [ 108-86-1 ]
  • [ 292638-85-8 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
98% With polystyrene-supported palladacycle catalyst; anhydrous Sodium acetate In N,N-dimethyl acetamide at 130℃; for 48h;
97% With anhydrous Sodium acetate In N,N-dimethyl acetamide at 130℃; for 48h;
95% With triethylamine In N,N-dimethyl-formamide at 120℃; for 6h;
95% With triethylamine In N,N-dimethyl-formamide at 120℃; for 6h; stereoselective reaction;
95% With 3,3'-(((4,5-dimethyl-1,2-phenylene)bis(azanediyl))bis(2-oxoethane-2,1-diyl))bis(1-methyl-1H-imidazol-3-ium) chloride; Cs2CO3; palladium (II) chloride In N,N-dimethyl-formamide at 125℃; for 3.5h; Schlenk technique; Inert atmosphere; regioselective reaction; 4.4. General procedure for the Mizoroki-Heck cross coupling reaction General procedure: In a Schlenk flask under N2 atmosphere, 2a (5 mg, 0.011 mmol), PdCl2 (2 mg, 0.011 mmol), Cs2CO3 (358 mg, 1,1 mmol) and DMF(1.5 mL) were added. The reaction mixture was heated at 90 °C for 30 min. Then, an aryl halide (1.0 mmol) and an olefin (1.2 mmol)were added and the mixture was further stirred at 125 °C under air atmosphere conditions. The reaction progress was monitored by Thin Layer Chromatography (EtOAc/hexane, 1:9). After completion of the reaction, the mixture was cooled to room temperature, and water (8 mL) was added and was extracted with EtOAc (3 10 mL).The organic solvent was dried over Na2SO4 and was evaporated under vacuum to give the crude product which was further purified by column chromatography using EtOAc/hexane, 1:9.
94% With 1,2,3,4,5-pentaphenyl-1′-(di-tert-butylphosphino)ferrocene; triethylamine; Palladium(0) bis(dibenzylideneacetone) In N,N-dimethyl-formamide at 20℃; for 20h;
94% With bis(2-hydroxyethyl)ammonium acetate; palladium (II) chloride at 100℃; for 16h;
94% With [Pd{C6H2-(CH2CH2NH2)-(OMe)2-3,4}Br(PPh3)]; potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 0.5h; General procedure for Heck reactions of aryl halides with olefins General procedure: To a round-bottom flask equipped with a magnetic stirring bar were added monomeric palladacycle 2 (0.4 mol %), K2CO3 (1.1 mmol), olefin (2.2 mmol) and aryl halide (1 mmol) in NMP (3 mL). The mixture was heated at 130 °C using an oil bath and the progress was monitored by TLC (hexane/EtOAc, 80:20) and gas chromatography (GC). After completing the reaction, the mixture was diluted with n-hexane (30 mL) and H2O. The organic layer was washed with brine (20 mL), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by recrystallization from EtOH and H2O. The products were characterized by comparing their mp and IR, 1H and 13C NMR spectra with those reported in the literature.
94% With potassium carbonate In water monomer; dimethyl sulfoxide at 90℃; for 10h; Green chemistry;
93% With (3,5-CH3-C6H-1,3-CH2P(i-Pr)2-CH2)Pd(OCOCF3); anhydrous sodium carbonate In various solvent(s) at 140℃; for 63h;
93% With CF3O3S(1-)*C52H46NO2P2Pd(1+); potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 0.0166667h; In air; Microwave irradiation; chemoselective reaction;
93% With palladium diacetate; Potassium bicarbonate at 140℃; for 0.166667h; Microwave irradiation; neat (no solvent); stereoselective reaction;
93% With {Pd[C6H2(CH2CH2NH2)-(OMe)(2),3,4] (μ-Br)}2; anhydrous Sodium acetate at 130℃; for 1.5h; Ionic liquid;
93% With potassium hydroxide In N,N-dimethyl-formamide at 80℃; for 10h; Inert atmosphere; Schlenk technique; General procedure for the Heck reaction General procedure: Palladium complex (1 or 2) (1.0 mmol), aryl halide (1.0 mmol), methyl acrylate (1.2 mol), base (4 mmol), and DMF (10 mL) were placed in a 100-ml Schlenk tube, and the reaction mixture was subjected to a freeze-thaw cycle before being heated at 80 °C for 10 h. Completion of the reaction was monitored in situ by use of gas chromatography after a specific time. After complete conversion, the reaction mixture was cooled and extracted with ethyl acetate-hexane. The extract was filtered through a pad of silica gel with copious washing, concentrated, and purifiedby flash chromatography on silica gel. Product purity was checked by NMR spectroscopy.
93% With C30H24N2NiO10; anhydrous sodium carbonate; hydrazine hydrate monohydrate In ethanol at 80℃; for 7h; Green chemistry;
93% With triethylamine In dimethyl sulfoxide at 100℃; for 1.5h;
92% With [Pd{C6H2(CH2CH2NH2)-(OMe)2,3,4}(μ-Br)]2; potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 3h; Inert atmosphere;
92% With C32H44N4O8P2Pd; potassium carbonate In N,N-dimethyl-formamide at 60℃; for 12h; Inert atmosphere; Schlenk technique; 3. Typical procedure Table 2: Heck reaction of aryl halides with olefins General procedure: A Schlenk tube was charged with readily prepared complex 6 (2 mol %) under a nitrogen atmosphere. Then styrene (104 mg, 1 mmol), K2CO3 (276 mg, 2 mmol) and dimethyl formamide (1 mL) were added at 25 °C. The reaction mixture was stirred under a nitrogen atmosphere. To this solution, bromobenzene (0.157 mg, 1 mmol) was then added with a syringe and the reaction mixture was heated at 60 °C in an oil bath for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with EtOAc, and filtered through a pad of Celite. The collected filtrate was then concentrated using a rotary evaporator, and the residue was purified by flash chromatography (10% EtOAc/hexane), which yielded 172 mg (96%) of trans-stilbene.
91% With anhydrous Sodium acetate In N,N-dimethyl-formamide at 130℃; for 24h;
91% With C54H42Cl2N4P2Pd2S2; potassium carbonate In N,N-dimethyl-formamide at 150℃; for 20h; General procedure: Typical Procedure for the Heck Reaction: The reaction vessel was charged with bromobenzene (1 mmol), alkene (2 mmol), K2CO3 (1.2 mmol), and the catalyst (1 mol %) in N,N-dimethylformamide (2 ml). The reaction mixture was heated to 150 °C, and the progress of reaction was monitored by TLC. At the end of the reaction, the reaction mixture was cooled to room temperature, diluted with EtOAc, and washed with 1 N aq HCl and water. The combined organic phase was dried over anhydrous Na2SO4. After removal of the solvent, the residue was subjected to column chromatography on silica gel using ethyl acetate and hexane mixtures to afford the coupled product in high purity.
91% With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h; Schlenk technique; stereoselective reaction; General procedure for Mizoroki-Heck couplingreactions General procedure: In a Schlenk flask, equipped with a magnetic stir bar,septum and a condenser were placed the aryl halide(1.0 mmol), olefin compound (1 mmol), K2CO3(2 mmol),catalyst (1 mol%) and DMF (5 mL). The flask wasimmersed in an oil bath and a reaction mixture stirred at100 °C. Upon complete consumption of starting materialsas determined by TLC analysis (petroleum ether/ethylacetate, 8:2), the catalyst was separated by filtration andwater (20 mL) was added. The filtrate was extracted withdiethyl ether (3 × 10 mL). The combined organic layer wascollected, dried over anhydrous Na2SO4and concentratedin vacuum, and the resulting compound was purified bycolumn chromatography.
91% With [PdBr2(PPh3)2]; potassium carbonate In N,N-dimethyl-formamide at 20 - 100℃; for 8h; Inert atmosphere; stereoselective reaction; Typical procedure for the Mizoroki-Heck reaction of aryl bromides with terminal olefins General procedure: In an oven-dried round bottom flask under an atmosphere of nitrogen at room temperature were placed complex 1 (0.0005 mmol) and DMF (3 mL). After stirring for 5 min, the aryl bromide (5 mmol), olefinic substrate (10 mmol) and K2CO3 (6 mmol) were introduced into the reaction flask. The reaction mixture was heated at 100 °C for the required reaction time under an atmosphere of nitrogen. At the end of the reaction, the reaction mixture was cooled to room temperature, diluted with EtOAc (20 mL), washed dil. HCl and water. The combined organic layer was dried over anhydrous Na2SO4 and stripped off the solvent under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and hexane mixtures to afford the Mizoroki-Heck product in high purity. The products were characterized by 1H NMR analysis
91% With dimethylammonium chloride; potassium carbonate In glycerol at 100℃; for 9h; Typical method for the Heck coupling reaction General procedure: To a mixture of aryl halide (1 mmol), alkene (1.2 mmol), and K2CO3 (2 mmol) in DES (DMAC:Gly, 3 mL), 0.018 g of GO-Fe3O4-Cellulose-Pd (0.75 mol%) was added. The mixture was stirred at 100 °C and the progress of reaction was checked by thin layer chromatography (TLC). The mixture was quenched with water (15 mL) after completing the reaction, and extracted with ethyl acetate (3 × 10 mL). The organic extract was dried over Na2SO4 and concentrated under vacuum. Purification of the obtained crude product was performed by column chromatography on silica gel. The aqueous phase, which contained both of the catalyst and DES, was used for another run after evaporation of water.
90% With {1-[3-(MeO)3Si(CH2)3]-3-Me-4-imidazolin-2-yl}2PdCl2; IL on SiO2; anhydrous Sodium acetate In 1-methyl-pyrrolidin-2-one at 140℃; for 24h;
90% With [CH3PPh3]2[Pd2Br2Cl4]; Sodium hydrogenocarbonate In N,N-dimethyl-formamide at 140℃; for 0.666667h;
90% With magnesium oxide; (S)-1-benzyl-3-((S)-1-hydroxy-3-phenylpropan-2-yl)-5-isobutyl-4,5-dihydro-1H-imidazol-3-ium chloride; potassium-t-butoxide; tetrabutylammonium bromide; palladium (II) chloride In N,N-dimethyl-formamide at 60℃; for 8h; General Procedure for Heck Reaction General procedure: To the mixture of imidazolium salt1 (0.4 % mmol) and PdCl2 (0.4 % mmol) in DMF (1mL) was added KOt-Bu (1.5 mmol), MgO (6mg), aryle halide (1mmol) and α, β unsaturated (3mmol) and allowed to react at 60 C. After completion of the reaction, the mixture was allowed to cool toroom temperature andthen was extracted with CH2Cl2(10 mL). The organic layer was dried over MgSO4. The solvent was removed under reduced pressure and the crude material was purified bycolumn chromatography using hexane/EtOAc (30:3) as an eluent to give the product.
90% With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h; Schlenk technique;
90% With C51H80N2O38Pd; potassium carbonate In water monomer; N,N-dimethyl-formamide at 80℃; for 12h; Schlenk technique; Green chemistry; 4.5. General procedure for Mizoroki-Heck cross-coupling reactionsof aryl halides with olefin using PdLnβ-CD (3a-3u) General procedure: A Schlenk flask equipped with asepta and a magnetic stir bar wasfilled with aryl halide (3.0 mmol), alkene (3.2 mmol), K2CO3(3.5 mmol) and PdLn-β-CD 3 mol% catalyst in water (5 mL pure orplain). The reaction was refluxed for the appropriate time underaerobic conditions. After completion of the reaction was confirmedby TLC, the reaction mixturewas cooled to room temperature.The solvent was removed by rotary evaporator and extraction of theproduct was carried out using ethyl acetate. The ethyl acetate fractionwas separated and dried over anhydrous sodium sulphate. Theresulting crude product was purified using flash column chromatographyof silica gel 60-120mesh with n-hexane/ethyl acetate (8:2ratio) as the eluent and afforded the pure desired product. After extractionof product, catalyst was simply reprecipitated from theaqueous layer by the addition of 10 mL of acetone. The recoveredcatalyst was filtered, washed with acetone (3 × 5 mL) and dried ina vacuum at 70 °C for 5 h and reused.
90% With triethylamine In water monomer; N,N-dimethyl-formamide at 130℃; for 2.5h; 2.3. General procedure for synthesis of trans-alkenes General procedure: In a typical method, 1 mmol of bromobenzene, 1 mmol of methylacrylate, 0.04 g of PdNPsPANI/silica-HNS, and 2 mmol of Et3N wereadded to 5 mL of DMF:H2O (1:1) and allowed to stirrer at 130 C. Thereaction completion was monitored by TLC (n-hexane and ethyl acetatemixture as solvent-5:1). After completion of the reaction, the reactionwas cooled to room temperature, the catalyst was removed by filtration.The catalyst was then washed with Et2O (3 5 mL). The organic layerwas separated and dried over anhydrous Na2SO4. The solvent wasevaporated under reduced pressure to give the corresponding arylolefins.To optimize the reaction conditions, GC was used to investigatethe yields under each condition. The NMR spectroscopic data of known compounds were found to be identical with those reported in the literature.
90% With tripotassium phosphate tribasic; tetrabutylammonium bromide; palladium diacetate; 2-benzothiazolecarboxaldehyde N,N-diphenylhydrazone In N,N-dimethyl acetamide for 1.5h; Irradiation;
90% With tetrabutylammonium bromide; potassium carbonate In water monomer at 100℃; for 5h; Green chemistry; General procedures for the Heck coupling reactions General procedure: A mixture of 4-iodoanisole (1 mmol), methyl acrylate (2 mmol), GO-PMMA-Pd catalyst (0.2 mol %), K2CO3 (1 mmol), TBAB (10 mol %) and 3ml water was stirred under 100 °C. The reaction took significant time for completion (Table. 3) and the progress of the reaction was monitored by TLC. After completion, the reaction mixture was extracted with ethyl acetate and washed with water repeatedly. The combined organic mixture was dried over anhydrous Na2SO4 and purified by column chromatography using petroleum ether/ethyl acetate as eluent to afford pure product. The catalyst was separated and washed for several times with ether and water. The recovered catalyst was used in next cycles and the isolated products were characterized by 1H and 13C NMR spectroscopy.
90% With triethylamine In neat (no solvent) at 20℃; for 0.383333h; Green chemistry; diastereoselective reaction; Typical Procedure for the Mizoroki-Heck Cross-Coupling Reaction General procedure: FMMWCNTs(at)CPA(at)SMTU(at)PdII NPs (IV) (0.35 mol-%,0.015 g) were added to a mixture of triethylamine (NEt3) (2 mmol, 0.202 g), methyl acrylate (1.2 mmol, 0.108 mL), and iodobenzene (1.0 mmol, 0.203 g) in solvent-free conditions at room temperature. After the completion of the reaction (15 min)which was monitored by TLC, the nanocatalyst was separated by a magnetic field, washed with ethyl acetate, and dried at room temperature for 24 h to be used in the next run. The reaction mixture was then extracted with ethyl acetate (55 mL) and the combined organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the crude product was purifiedby TLC (or column chromatography using n-hexane/ethylacetate (50 : 1)) using n-hexane/ethyl acetate (8 : 2) to produce the pure methyl cinnamate (0.153 g, 98% yield).
89% With tetrabutylammonium bromide; potassium carbonate In 1-methyl-pyrrolidin-2-one at 140℃; for 12h;
88% With tripotassium phosphate tribasic; C21H15N3O3Pd In water monomer at 130℃; for 4h; Sealed tube;
88% With sodium lauryl sulfate; potassium carbonate In water monomer at 100℃; for 8h; Green chemistry; 3.3. General procedure for the catalytic Mizoroki-Heck coupling General procedure: In a round bottom flask (5 mL) equipped with condenser andmechanical stirrer, aryl halide (1.0 mmol), olefin (1.1 mmol), K2CO3(1 mmol), SDS (0.4 mmol, 0.1 gr), water (3 mL) and G3-Gu-Pdcatalyst (10 mg, 0.8 mol% of palladium content) were added. Then,temperature raised to 100 °C in an oil bath and reaction progresswas checked by TLC during the reaction mixture stirred andrefluxed for the specific time (Table 3). After cooling the reactionmixture, G3-Gu-Pd catalyst was recovered by the external magnetand the resulting product was extracted with ethyl acetate (3x5 mL). Then extracted organic layer was dried over Na2SO4. Afterevaporating the solvent by vacuum distillation, and purifying withsilica gel column chromatography employing n-hexane/ethyl acetateeluent, pure corresponding product was obtained. All of thesynthesized products were characterized by melting point, 1HNMR, 13C NMR, IR spectroscopy and elemental analysis (See supportingInformation). The data for all compounds were in accordancewith to those reported in the other referenced literature.
87% With tetrabutylammonium bromide; anhydrous Sodium acetate; Pd(L-proline)2 In water monomer at 135℃; for 0.583333h; Microwave irradiation;
87% With Sodium hydrogenocarbonate In 1-methyl-pyrrolidin-2-one at 140℃; for 0.666667h;
86% With 0.26% Pd/TiO2; anhydrous potassium acetate In N,N-dimethyl acetamide at 140℃; for 24h; Inert atmosphere;
86.3% With 3C12H24KO6*O4P(3-); potassium carbonate; palladium (II) chloride In water monomer; N,N-dimethyl-formamide at 140℃; for 1.25h;
86% With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 12h;
86% With C26H24N6NiS2; potassium carbonate In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere; Typical procedure for the Mizoroki-Heckreaction of aryl bromides with terminal olefins General procedure: In an oven-dried round bottom flask under an atmosphere of nitrogen atroom temperature were placed complex 1(25 mmol)and DMF (5 mL). After stirringfor 5 min, the aryl bromide (5 mmol), olefinic substrate (10 mmol) and K2CO3(6 mmol) were introduced into the reaction flask. The reaction mixture washeated at 110 °C for 24 h under an atmosphere of nitrogen. At the end of thereaction, the reaction mixture was cooled to room temperature, diluted withEtOAc (20 mL), washed dil. HCl and water. The combined organic layer was dried over anhydrous Na2SO4and stripped off the solvent under reduced pressure. The residue was subjectedto column chromatography on silica gel using ethyl acetate and hexane mixturesto afford the Mizoroki-Heck product in high purity. The products werecharacterized by 1H-NMR analysis.
86% With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h; 4.2. General procedure for the Heck reaction using the Pd-NHC-MIL-101(Cr) catalyst General procedure: A conical flask (10 mL) was charged with aryl halide (1.0 mmol), terminal alkene (1.1 mmol), K 2 CO 3 (2 mmol, 0.28 g), Pd-NHC-MIL- 101(Cr) catalyst (0.8 mol %, 6.5 mg) and DMF (5 mL). The mixture was heated in an oil bath at 110 °C. Upon completion of the reac- tion monitored by GC or TLC analysis ( Scheme 2 ), the mixture was filtered and the organic layer was cooled to room temperature and then water added. The organic layer was extracted with ethyl ac- etate (3 ×5 mL) and dried over Na 2 SO 4 . The solvent was removed under reduced pressure and the product was purified by silica gel column chromatography employing n -hexane/ethyl acetate as the eluent, affording the pure corresponding product.
85% With [K2(H2O)3{(H2O)0.5(at)decamethylcucurbit[5]uril}][PdCl4]; anhydrous sodium carbonate In N,N-dimethyl-formamide at 140℃; for 24h;
85% With tripotassium phosphate tribasic In water monomer at 80℃; for 1.66667h;
85% With triethylamine In N,N-dimethyl-formamide at 110℃; for 2h;
85% With Cs2CO3 In water monomer at 100℃; for 1.66667h; Green chemistry;
83% With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 8h;
82% With triethylamine In acetonitrile for 24h; Heating;
82% With C36H26ClN2O2PPd; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 10h; Inert atmosphere; Typical procedure for the Mizoroki-Heck reaction of aryl bromides with terminal olefins General procedure: In an oven-dried round bottom flask under an atmosphere of nitrogen at room temperature were placed complex 1 (25 mol) and DMF (5 mL). After stirring for 5 min, the aryl bromide (5 mmol), olefinic substrate (10 mmol) and K2CO3 (6 mmol) were introduced into the reaction flask. The reaction mixture was heated at 100 °C for 10 h under an atmosphere of nitrogen. At the end of the reaction, the reaction mixture was cooled to room temperature, diluted with EtOAc (20 mL), washed dil. HCl and water. The combined organic layer was dried over anhydrous Na2SO4 and stripped off the solvent under reduced pressure.The residue was subjected to column chromatography on silica gel using ethyl acetate and hexane mixtures to afford the Mizoroki-Heck product in high purity. The products were characterized by 1H-NMR analysis.
82% With anhydrous sodium carbonate In N,N-dimethyl-formamide at 100℃; for 12h; 3.2.5. General procedure for heck reaction General procedure: A round bottom flask was charged with aryl halide (15 mmol), olefins such as methyl and methyl methacrylate and acrylonitrile (15 mmol) using DMF as a solvent (100 mL), Then Na2CO3 as base (15 mmol) and catalyst (0.5 mol %) were added. The stirring solution was refluxed at 100°C for 12 h. After requisite time, the reaction mixture was cooled to room temperature. The palladium catalyst was separated from the mixture by filtration. The solution diluted with water (30 mL) and product extracted with ethyl acetate (3×10 mL). Then, the product was concentrated under reduced pressure. This product was purified and crystallized with ethanol and water (1:1).

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[5]Takallou, Ahmad; Habibi, Azizollah; Halimehjani, Azim Ziyaei; Balalaie, Saeed [Journal of Organometallic Chemistry, 2019, vol. 888, p. 24 - 28]
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[9]Puthiaraj, Pillaiyar; Pitchumani, Kasi [Green Chemistry, 2014, vol. 16, # 9, p. 4223 - 4233]
[10]Ohff; Ohff; Van der Boom; Milstein [Journal of the American Chemical Society, 1997, vol. 119, # 48, p. 11687 - 11688]
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[12]Location in patent: experimental part Valizadeh, Hassan; Vaghefi, Sevil [Heterocyclic Communications, 2010, vol. 16, # 2-3, p. 113 - 120]
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[18]Shaikh, Tanveer Mahamadali; Hong, Fung-E [Beilstein Journal of Organic Chemistry, 2013, vol. 9, p. 1578 - 1588]
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  • 21
  • [ 103-26-4 ]
  • [ 81290-20-2 ]
  • (E)-1,1,1-trifluoro-4-phenyl-3-buten-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% Stage #1: Methyl cinnamate; (trifluoromethyl)trimethylsilane With tetrabutyl ammonium fluoride In tetrahydrofuran; pentane at 0 - 20℃; for 18h; Inert atmosphere; Stage #2: With hydrogenchloride In tetrahydrofuran; water for 10h; Inert atmosphere;
85% With tetrabutyl ammonium fluoride In tetrahydrofuran; pentane for 24h; Ambient temperature;
68% Stage #1: Methyl cinnamate; (trifluoromethyl)trimethylsilane With tetrabutyl ammonium fluoride In tetrahydrofuran; hexane at 0 - 25℃; for 16h; Stage #2: With hydrogenchloride In tetrahydrofuran; water at 20 - 25℃; for 10h;
68% With tetrabutyl ammonium fluoride In tetrahydrofuran; hexane at 0 - 20℃; for 16h;
84 % Spectr. Stage #1: Methyl cinnamate; (trifluoromethyl)trimethylsilane With tetrabutylammonium acetate In toluene at 0 - 20℃; for 1h; Stage #2: With hydrogenchloride In tetrahydrofuran; toluene

  • 22
  • [ 292638-85-8 ]
  • [ 108-90-7 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
93% With CF3O3S(1-)*C52H46NO2P2Pd(1+); potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 0.0666667h; In air; Microwave irradiation; chemoselective reaction;
92% With N,N-dimethylammonium chloride; potassium carbonate In glycerol at 100℃; for 20h; Typical method for the Heck coupling reaction General procedure: To a mixture of aryl halide (1 mmol), alkene (1.2 mmol), and K2CO3 (2 mmol) in DES (DMAC:Gly, 3 mL), 0.018 g of GO-Fe3O4-Cellulose-Pd (0.75 mol%) was added. The mixture was stirred at 100 °C and the progress of reaction was checked by thin layer chromatography (TLC). The mixture was quenched with water (15 mL) after completing the reaction, and extracted with ethyl acetate (3 × 10 mL). The organic extract was dried over Na2SO4 and concentrated under vacuum. Purification of the obtained crude product was performed by column chromatography on silica gel. The aqueous phase, which contained both of the catalyst and DES, was used for another run after evaporation of water.
91% With C50H58Cl2N6Pd; triethylamine; calcium chloride In water; N,N-dimethyl-formamide at 90℃; for 3h; 4.2. Heck-Mizoroki coupling reactions General procedure: A 25 mL RB flask was charged with chloroarene (1.00 mmol),methyl acrylate (0.130 g, 1.50 mmol), triethylamine (0.152 g,1.50 mmol), and DMF (5 mL). A DMF solution of catalysts (0.1,0.01, and 0.001 mol %, Table 1; 0.01 mol %, Table 2) was added tothe aforementioned solution via the syringe. The flask was fittedto a water condenser capped with anhydrous CaCl2 guard tubeand the contents in the flask were simultaneously stirred andheated at 90 C for 3 h. The reaction mixture was cooled and subsequentlypoured into distilled water (300 mL). The product wasextracted with EtOAc (5 50 mL). The organic layer was dried overanhydrous sodium sulfate and concentrated under vacuum to giveoil. The oil was purified by column chromatography on silica gel(n-hexane/EtOAc, 10/0 ?8/2, v/v) to afford coupling products inyields indicated in Tables 1 and 2.
90% With {Pd[C6H2(CH2CH2NH2)-(OMe)(2),3,4] (μ-Br)}2; sodium acetate at 130℃; for 0.0666667h; Microwave irradiation; Ionic liquid;
85% With [Pd{C6H2-(CH2CH2NH2)-(OMe)2-3,4}Br(PPh3)]; potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 1.16667h; General procedure for Heck reactions of aryl halides with olefins General procedure: To a round-bottom flask equipped with a magnetic stirring bar were added monomeric palladacycle 2 (0.4 mol %), K2CO3 (1.1 mmol), olefin (2.2 mmol) and aryl halide (1 mmol) in NMP (3 mL). The mixture was heated at 130 °C using an oil bath and the progress was monitored by TLC (hexane/EtOAc, 80:20) and gas chromatography (GC). After completing the reaction, the mixture was diluted with n-hexane (30 mL) and H2O. The organic layer was washed with brine (20 mL), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by recrystallization from EtOH and H2O. The products were characterized by comparing their mp and IR, 1H and 13C NMR spectra with those reported in the literature.
82% With potassium carbonate In neat (no solvent) at 40℃; for 2h; Irradiation;
80% With triethylamine In neat (no solvent) at 20℃; for 0.583333h; Green chemistry; diastereoselective reaction; Typical Procedure for the Mizoroki-Heck Cross-Coupling Reaction General procedure: FMMWCNTs(at)CPA(at)SMTU(at)PdII NPs (IV) (0.35 mol-%,0.015 g) were added to a mixture of triethylamine (NEt3) (2 mmol, 0.202 g), methyl acrylate (1.2 mmol, 0.108 mL), and iodobenzene (1.0 mmol, 0.203 g) in solvent-free conditions at room temperature. After the completion of the reaction (15 min)which was monitored by TLC, the nanocatalyst was separated by a magnetic field, washed with ethyl acetate, and dried at room temperature for 24 h to be used in the next run. The reaction mixture was then extracted with ethyl acetate (55 mL) and the combined organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the crude product was purifiedby TLC (or column chromatography using n-hexane/ethylacetate (50 : 1)) using n-hexane/ethyl acetate (8 : 2) to produce the pure methyl cinnamate (0.153 g, 98% yield).
76% With tri-tert-butyl phosphine; caesium carbonate In 1,4-dioxane at 100℃; for 42h;
76% With tri-tert-butyl phosphine; caesium carbonate In 1,4-dioxane at 100℃; for 42h; Heck reaction of aryl chlorides with methyl acrylate and styrene; effect of the solvent, phosphine, base on the rate of Pd-catalyzed Heck coupling;
75% With sodium hydrogencarbonate In 1-methyl-pyrrolidin-2-one at 160℃; for 11h;
75% With 4-amino-1-(2,3-dihydroxypropyl)pyridinium hydroxide; palladium diacetate In water at 100℃; for 8h;
73% With triethylamine In dimethyl sulfoxide at 100℃; for 4h;
69% With palladium diacetate; potassium hydrogencarbonate at 140℃; for 0.416667h; Microwave irradiation; neat (no solvent); stereoselective reaction;
59% With C16H30Cl2N4P2Pd; potassium carbonate In N,N-dimethyl-formamide at 110℃; for 24h; 2.1 General procedure for Mizoroki-Heck reaction of aryl halide and olefins catalyzed by palladium complexes General procedure: To a 25 mL Schlenk tube aryl halides 1 (0.2 mmol), olefins 2 (0.3 mmol, 1.5 equiv), K2CO3 (0.4 mmol, 2 equiv), Pd complexes (5 mol%) and DMF (1.0 mL) was added. Then the tube was sealed and stirred at 110 for 24h. After completion, the mixture was extracted with ethyl acetate (3×10 mL) and dried by anhydrous sodium sulfate. The volatile component was removed under vacuum and the residues were further purified by preparative thin layer chromatography (ethyl acetate/petroleum ether = 1:6) to deliver corresponding products 3.
55% With 3,3'-(((4,5-dimethyl-1,2-phenylene)bis(azanediyl))bis(2-oxoethane-2,1-diyl))bis(1-methyl-1H-imidazol-3-ium) chloride; caesium carbonate; palladium dichloride In N,N-dimethyl-formamide at 125℃; for 15h; Schlenk technique; Inert atmosphere; 4.4. General procedure for the Mizoroki-Heck cross coupling reaction General procedure: In a Schlenk flask under N2 atmosphere, 2a (5 mg, 0.011 mmol), PdCl2 (2 mg, 0.011 mmol), Cs2CO3 (358 mg, 1,1 mmol) and DMF(1.5 mL) were added. The reaction mixture was heated at 90 °C for 30 min. Then, an aryl halide (1.0 mmol) and an olefin (1.2 mmol)were added and the mixture was further stirred at 125 °C under air atmosphere conditions. The reaction progress was monitored by Thin Layer Chromatography (EtOAc/hexane, 1:9). After completion of the reaction, the mixture was cooled to room temperature, and water (8 mL) was added and was extracted with EtOAc (3 10 mL).The organic solvent was dried over Na2SO4 and was evaporated under vacuum to give the crude product which was further purified by column chromatography using EtOAc/hexane, 1:9.
50% With [CH3PPh3]2[Pd2Br2Cl4]; sodium hydrogencarbonate In N,N-dimethyl-formamide at 140℃; for 24h;
40% With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 12h; Schlenk technique; stereoselective reaction; General procedure for Mizoroki-Heck couplingreactions General procedure: In a Schlenk flask, equipped with a magnetic stir bar,septum and a condenser were placed the aryl halide(1.0 mmol), olefin compound (1 mmol), K2CO3(2 mmol),catalyst (1 mol%) and DMF (5 mL). The flask wasimmersed in an oil bath and a reaction mixture stirred at100 °C. Upon complete consumption of starting materialsas determined by TLC analysis (petroleum ether/ethylacetate, 8:2), the catalyst was separated by filtration andwater (20 mL) was added. The filtrate was extracted withdiethyl ether (3 × 10 mL). The combined organic layer wascollected, dried over anhydrous Na2SO4and concentratedin vacuum, and the resulting compound was purified bycolumn chromatography.
27% With 0.26% Pd/TiO2; tetrabutylammomium bromide; potassium acetate In N,N-dimethyl acetamide at 150℃; for 36h; Inert atmosphere;
25% With potassium phosphate In water at 80℃; for 4h;
25% With triethylamine In N,N-dimethyl-formamide at 140℃; for 3h; Sealed tube; Inert atmosphere; Green chemistry; 2.2. General procedure for Heck reaction General procedure: To a dried sealed tube, aryl halide (0.25 mmol), activated alkene(0.3 mmol), Na2CO3 (0.75 mmol), polymer supported palladium catalyst(2 mol%) were added followed by the addition of DMF (2 ml). Thereaction mixture was then stirred at 120 °C under N2 atmosphere andprogress of the reaction was monitored by TLC. After completion of thereaction (3 h), the reaction mixture was extracted with ethyl acetateand water. The organic layer was separated and dried over anhydrousNa2CO3 and concentrated on rotary evaporator. The obtained crudeproduct was separated by column chromatography using appropriateEthylacetate/Hexanemixture (85 to 95: 15 to 5) and the yields werenoted. The structure of the products was characterized using spectroscopicanalyses and in comparison with literature data. Representative data for compound (3a): Colourless Liquid.Rf = 0.47 (Hexane/EtOAc = 95:5).1H NMR (400 MHz, CDCl3): δ 7.64(d, J = 16 Hz, 1H), 7.45-7.43 (m, 2H), 7.31-7.29 (m, 3H), 6.38 (d,J = 16 Hz, 1H), 3.73 (s, 3H).13C NMR (100 MHz, CDCl3): δ.167.2,144.8, 134.4, 130.3, 128.8, 128.1, 117.7, 51.7. FTIR (neat): 2947,1711, 1636, 1313, 1274 cm-1. GC-MS (EI) [M]+: m/z calculated forC10H10O2:162.1, found:162.1
24% With potassium phosphate; C21H15N3O3Pd In water at 130℃; for 4h; Sealed tube;
With triethylamine In N,N-dimethyl acetamide at 120℃; for 70h;
With sodium carbonate; triethylamine In 1-methyl-pyrrolidin-2-one at 160℃; for 18h;
7 %Chromat. With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 24h;
86 %Chromat. With 1-glycyl-3methyl imidazolium chloride - palladium(II) complex; triethylamine at 25℃; for 15h; neat (no solvent);
With bis(triphenylphosphine)palladium(0); caesium carbonate In 1,4-dioxane at 95℃; for 22h; Inert atmosphere; Schlenk technique;
With C29H28N4O2Pd2S; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 1.16667h; stereoselective reaction; 2.6. General procedure for the Heck cross-coupling reaction General procedure: In a round-bottom flask equipped with a magnetic stir bar, arylhalide (1.5 mmol), olefine (1 mmol), potassium carbonate(1 mmol), catalysts 1-4 (0.02 mmol) and DMF (2 mL) were addedand heated at 100 C. The mixture was vigorously stirred underthese reaction conditions and completion of the reaction was monitoredby TLC (Ethyl acetate: n-hexane, 25:75).In each case, after completion of the reaction, the reaction mixturewas cooled to room temperature. Then, Ethyl acetate (5 mL)and water (10 mL) were added. The aqueous layer was furtherextracted by ethyl acetate (2 * 5 mL). The combined organic layerswere washed with saturated brine for two times, dried overMgSO4, filtered, and concentrated to give the desired product.

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[7]Ghasemzadeh, Maryam Sadat; Akhlaghinia, Batool [Australian Journal of Chemistry, 2019, vol. 72, # 9, p. 674 - 692]
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[25]Location in patent: experimental part Karthikeyan, Parasuraman; Muskawar, Prashant Narayan; Aswar, Sachin Arunrao; Bhagat, Pundlik Rambhau; Sythana, Suresh Kumar [Journal of Molecular Catalysis A: Chemical, 2012, vol. 358, p. 112 - 120]
[26]Fraser, Andrew W.; Jaksic, Bryan E.; Batcup, Rhys; Sarsons, Christopher D.; Woolman, Michael; Baird, Michael C. [Organometallics, 2013, vol. 32, # 1, p. 9 - 11]
[27]Khadir, Narjes; Tavakoli, Ghazal; Assoud, Abdeljalil; Bagherzadeh, Mojtaba; Boghaei, Davar M. [Inorganica Chimica Acta, 2016, vol. 440, p. 107 - 117]
  • 23
  • [ 103-26-4 ]
  • [ 4407-36-7 ]
YieldReaction ConditionsOperation in experiment
94% With N-methylpyrrolidine zinc borohydride In tetrahydrofuran at 20℃; for 1.08333h;
93% With C15H29MnNO3P2(1+)*Br(1-); potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 110℃; for 24h; Inert atmosphere; Autoclave;
93.9% With methanol; diisobutylaluminium hydride In hexane; dichloromethane at -78 - 20℃; for 2h; Inert atmosphere; 1.II 1. Synthesis Process I Step (II): 3-phenyl-acrylic acid, methyl ester (D011b, 4 g, 24.7 mmol, 1 eq) was added into a 500 ml round bottom flask filled with N2 gas and was dissolved in anhydrous dichloromethane and then placed in a low-temperature reactor set at -78° C. Diisobutylaluminium hydride 1M solution (DIBAL-H; 1M solution in hexane, 74 ml, 74.0 mmol, 3 eq) was slowly added dropwise over 30 minutes to the reaction solution and methanol (22 ml) was slowly added dropwise while the reaction temperature was raised to 0° C. and stirring was carried out for 1 hour. The reaction solution was transferred to room temperature, stirred for 30 minutes and then a saturated aqueous solution of Rochelle's salt (88 ml) was added thereto. The reaction mixture was vigorously stirred at room temperature for 2 hours, and the mixture was partitioned twice with dichloromethane (300 ml) and distilled water (300 ml) to collect the organic layers and was dehydrated with sodium sulfate, filtered and the resulting filtrate was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (ethyl acetate:n-hexane=3:1) to obtain the pure product 3-phenyl-pro-2-pen-1-ol (D011c, 3.1 g, yield=93.9%, Rf=0.37 (2:1 n-hexane-ethyl acetate) to apply to the next step.
80% Stage #1: Methyl cinnamate With sodium triethylborohydride In diethyl ether; toluene at 20℃; for 5h; Inert atmosphere; Stage #2: With sodium hydroxide In methanol; diethyl ether; toluene at 20℃; for 2h;
With sodium hydroxide; sodium tetrahydroborate; zinc 2-ethylhexanoate 1.) THF, 70 deg C, 4 h, 2.) 40 deg, 1 h; Yield given; Multistep reaction;
65 % Chromat. With sodium tetrahydroborate In diethylene glycol dimethyl ether at 162℃; for 5h;
Stage #1: Methyl cinnamate With diisobutylaluminium hydride In hexane; dichloromethane at -78 - 0℃; for 1h; Inert atmosphere; Stage #2: With methanol In hexane; dichloromethane at 20℃; for 0.5h; Inert atmosphere;
Stage #1: Methyl cinnamate With diisobutylaluminium hydride In tetrahydrofuran; toluene at -78℃; for 2.7h; Inert atmosphere; Stage #2: With hydrogenchloride; water; ammonium chloride In tetrahydrofuran; toluene 1.A Example 1 : Synthesis of compounds according to the invention and intermediatesSynthesis of cinnamic aldehydesFor the synthesis of cinnamic aldehydes two different methods (A and B) were used.Method A:50.0 mmol of the corresponding cinnamic acid were dissolved in 200 ml methanol. The solution was rinsed with HCI gas for 15 min and then stirred at room temperature over night. The solvent was evaporated in vacuo and the ester was extracted with ethyl acetate. The ui yai liU layci vvass νναοι icu vvi u I >j /ς anu ui inc, ui iou υν υι uu ium oun ato anu evaporated in vacuo.13 mmol of the so-obtained methyl ester were dissolved in 80 ml THF (dried over sodium) under argon atmosphere. The solution was cooled down to -78°C. 40 mmol of an 1 M DIBAL-H solution in toluene were injected during 40 min. The reaction solution was then stirred for 2 h at -78°C. Careful adding of 70 ml 10% NH4CI obtained a gelatinous substance, which was dissoived in 2N HCI. The product was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and evaporated in vacuo, 1 1 .5 mmol of the so-obtained alcohol were dissolved in 20 ml toluene. 69 mmol Mn02 were added, and the solution was stirred at room temperature for 30 h. The solution was filtered twice to remove anorganic parts, and the solvent was evaporated in vacuo. The desired product was purified by using column chromatography
Stage #1: Methyl cinnamate With diisobutylaluminium hydride In dichloromethane at -78℃; for 0.5h; Inert atmosphere; Stage #2: In dichloromethane at -78 - 0℃; for 1h; Inert atmosphere; General procedure: To a solution of the ester in dichloromethane (20 mL) at 78 Cwas added DIBAL (1Min dichloromethane, 25 mL, 25 mmol) in one portion. After 30 min stirring at 78 C, the solution was slowlywarmed to 0 C and stirred for 1 h, then cooled to 78 C. The reactionwasquenched by dropwise addition of 1 Naqueous HCl. Afterwarming to RT, additional 6N HCl and dichloromethane were addedcarefully until complete dissolution of the precipitate. The aqueousphase was extracted twice with dichloromethane and combinedorganic phases were dried over Na2SO4. Subsequent solvent removalunder reduced pressure gave the title alcohol as an off-white solid(78e82% yield), which did not require further purification.
90 %Chromat. With [Ru(2-(methylthio)-N-[(pyridin-2-yl)methyl]ethan-1-amine)(triphenylphosphine)Cl2]; potassium <i>tert</i>-butylate; hydrogen In dodecane; toluene at 40℃; for 4h; Autoclave; 18a Hvdroqenation of cinnamate esters General procedure: A 100 mL hastelloy autoclave with mechanical stirrer was charged with the catalyst of example 9 (23 mg, 0.038 mmol, 0.25 mol%), substrate (15 mmol), 30 mL of toluene, freshly sublimed KOtBu (41 mg, 0.38 mmol, 2.5 mol%), and 1000 μΙ of anhydrous n- dodecane under an argon atmosphere. The autoclave vessel was flushed with nitrogen three times, and with hydrogen two times, then pressurized to 30 bar H2, heated to 40°C and stirred for 4 hours. During the reaction time the pressure was kept at 30 bar H2. The products are determined based on GC analysis retention time. The given values for conversion (C), yield (Y), and selectivity (S) [%] are mol% with regard to the initial cinnamyl ester amount, and corrected by n-dodecane. The results are summarized in the following table.
With diisobutylaluminium hydride In dichloromethane at -78 - 0℃; for 4h;
Multi-step reaction with 2 steps 1: 3C7H21Si3(1-)*La(3+) / benzene / 0.5 h / 25 °C / Inert atmosphere 2: sodium hydroxide; water / Inert atmosphere
With diisobutylaluminium hydride In dichloromethane; toluene at -78 - 0℃; for 1h; Inert atmosphere; 2.2 2.2 Method for the synthesis of 3-(7S)-(+)-8,8-dimethyl-7-(3-phenyl-allyloxy)-7,8-dihydro-6H-pyrano[3,2-g]chromen-2-one (2, KC2) To synthesize KC-2, a solution of trans-cinnamic acid (1a, 34.2mM, 1eq) and concentrated sulfuric acid (five drops) in MeOH (20mL) was warmed to reflux overnight. After cooling to room temperature, the solvent was removed under reduced pressure and the residue was purified using flash silica gel column chromatography to obtain 3-phenyl-acrylic acid methyl ester (2b). A solution of 3-phenyl-acrylic acid methyl ester (2b, 24.7mM) in dichloromethane anhydrous was cooled to -78°C under nitrogen gas. Then, the mixture was slowly added to a 1M solution of diisobutylalluminum hydride (DIBAL-H) in toluene (74mM). After stirring the mixture at 0°C for 1h, it was added to methanol (22mL) and stirred at room temperature for 30min. Then, aqueous saturated Rochelle’s salt (88mL) was added to the mixture and it was vigorously stirred for 2h. The reaction mixture was separated with dichloromethane and dried sodium sulfate and the solvent was removed under reduced pressure. The residue was purified by flash silica gel column chromatography to obtain 3-phenyl-pro-2-pen-1-ol (2c, 7.45mM), which was then dissolved in dichloromethane anhydrous and added to a 1M solution of boron tribromide in dichloromethane (2.61mM) in an ice bath for 1h. Next, the mixture was added to ice water (50mL) and stirred for 10min. Subsequently, the reaction mixture was separated using saturated sodium bicarbonate and diethyl ether, the organic layer was dried with sodium sulfate and concentrated in vacuo, and the residue was purified using flash silica gel column chromatography to obtain (3-bromo-prophenyl)-benzene (2d).
With aluminum (III) chloride; lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 4h;
With diisobutylaluminium hydride In dichloromethane at 0 - 20℃; Inert atmosphere;

Reference: [1]Tajbakhsh; Lakouraj; Mohanazadeh; Ahmadi-Nejhad [Synthetic Communications, 2003, vol. 33, # 2, p. 229 - 236]
[2]Elangovan, Saravanakumar; Garbe, Marcel; Jiao, Haijun; Spannenberg, Anke; Junge, Kathrin; Beller, Matthias [Angewandte Chemie - International Edition, 2016, vol. 55, # 49, p. 15364 - 15368][Angew. Chem., 2016, # 128, p. 15590 - 15594]
[3]Current Patent Assignee: KOREA UNIVERSITY - US2020/48274, 2020, A1 Location in patent: Paragraph 0051-0055
[4]Peng, Dongjie; Zhang, Mintao; Huang, Zheng [Chemistry - A European Journal, 2015, vol. 21, # 42, p. 14737 - 14741]
[5]Mimoun [Journal of Organic Chemistry, 1999, vol. 64, # 7, p. 2582 - 2589]
[6]Zhu, Hua-Jie; Pittman Jr., Charles U. [Synthetic Communications, 2003, vol. 33, # 10, p. 1733 - 1750]
[7]Location in patent: experimental part Lee, Kyeong; Lee, Jee-Hyun; Boovanahalli, Shanthaveerappa K.; Choi, Yongseok; Choo, Soo-Jin; Yoo, Ick-Dong; Kim, Dong Hee; Yun, Mi Young; Lee, Gye Won; Song, Gyu-Yong [European Journal of Medicinal Chemistry, 2010, vol. 45, # 12, p. 5567 - 5575]
[8]Current Patent Assignee: MEDICAL UNIVERSITY OF VIENNA - WO2012/13725, 2012, A1 Location in patent: Page/Page column 36-37
[9]Maity, Arnab Kumar; Chatterjee, Paresh Nath; Roy, Sujit [Tetrahedron, 2013, vol. 69, # 2, p. 942 - 956]
[10]Current Patent Assignee: KONINKLIJKE DSM N.V. - WO2017/194663, 2017, A1 Location in patent: Page/Page column 17; 39
[11]Bao, Xia-Zhen; Dai, Fang; Wang, Qi; Jin, Xiao-Ling; Zhou, Bo [Free Radical Biology and Medicine, 2019, vol. 134, p. 406 - 418]
[12]Patnaik, Smita; Sadow, Aaron D. [Angewandte Chemie - International Edition, 2019, vol. 58, # 8, p. 2505 - 2509][Angew. Chem., 2019, vol. 131, # 8, p. 2527 - 2531,5]
[13]Lee, Wonhwa; Yuseok; Lee, Changhun; Jeong, So Yeon; Lee, Jee-Hyun; Baek, Moon-Chang; Song, Gyu-Yong; Bae, Jong-Sup [Biochemical Pharmacology, 2019, vol. 163, p. 260 - 268]
[14]Patra, Debabrata; Panja, Subir; Saha, Amit [European Journal of Organic Chemistry, 2020, vol. 2020, # 7, p. 878 - 883]
[15]Carlet, Federica; Bertarini, Greta; Broggini, Gianluigi; Pradal, Alexandre; Poli, Giovanni [European Journal of Organic Chemistry, 2021, vol. 2021, # 15, p. 2162 - 2168]
  • 24
  • [ 140-10-3 ]
  • [ 77-78-1 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate In acetone at 80℃; for 6h; 4.10. Preparation of methyl cinnamate (20) To a solution of (E)-cinnamic acid (7, 5.1 g) in 50 mL of acetone, 23.7 g of K2CO3 and 3.25 mL of dimethyl sulfate were added. The mixture was stirred at 80 °C for 6 h. The mixture was then filtered to remove K2CO3. The filtrate was acidified with 1 M of hydrochloric acid and was extracted with ethyl acetate. The organic layer was washed with water and brine, dried with anhydrous magnesium sulfate, filtered and evaporated to afford methyl (E)-cinnamate (20, 4.6 g, 90%).Methyl cinnamate (20): IR νmax (film) 3062, 2950, 1716 cm-1; 1H NMR (CD3OD, 500 MHz): δ 7.65 (1H, d, J = 15.9 Hz; H-3), 7.56-7.35 (5H, m; aromatic), 6.48 (1H, d, J = 15.9 Hz; H-2), 3.75 (3H, s; COOCH3); EIMS m/z 162 [M]+, 131 (base).
86% With lithium hydroxide In tetrahydrofuran for 0.5h; Heating;
With potassium carbonate In acetone at 20 - 50℃; for 5h;
  • 25
  • (2S,3R)-2,3-Dibromo-3-phenyl-propionic acid methyl ester [ No CAS ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
94% With bismuth(III) chloride; gallium In tetrahydrofuran at 20℃; for 0.5h; stereoselective reaction;
92% With indium; cobalt(II) chloride hexahydrate In methanol at 20℃; for 0.5h; chemoselective reaction;
92% With indium; niobium pentachloride In tetrahydrofuran at 20℃; for 0.166667h; Sonication; chemoselective reaction; A typical procedure for the debromination of vic-dibromides is as follows: General procedure: Indium powder (230 mg, 2.0 mmol) and NbCl5 (238 mg,1.0 mmol) are mixed in THF (4 mL). The resulting mixture is sonicated in an ultrasonic cleaner9 for 30 min and a solution of the low-valent niobium-indium complex is formed. 1,2-Dibromo-1,2-diphenylethane (170 mg, 0.5 mmol) is then added to this solution and the reaction mixture is stirred for 15 min at room temperature. The solvent is removed under reduced pressure and the residue is extracted with ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. The crude product is purified by silica gel column chromatography (hexane:ethyl acetate = 10:1) to afford trans-stilbene (85 mg, 94%).
91% With gallium; bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at 20℃; for 0.166667h; Inert atmosphere; Ultrasonic irradiation; chemoselective reaction;
91% at 20℃; for 0.05h; chemoselective reaction; General Procedure for the Reaction General procedure: A 10-mL round-bottomed flask was charged with indiumpowder (230 mg, 2.0 mmol), vanadium trichloride (157 mg,1.0 mmol) and THF (4 mL). The resulting mixture was stirred for 30 min under sonication producing a solution ofthe low-valent vanadium-indium complex. 1,2-Dibromo-1,2-diphenylethane (170 mg, 0.5 mmol) was then added tothis solution and the reaction mixture was stirred for 3 minat room temperature. The progress of the reaction was monitoredby TLC. After completion of the reaction, the solventwas removed under reduced pressure and the residuewas then extracted with ethyl acetate (3 × 10 mL). The combinedextract was washed with brine, dried over anhydrousNa2SO4 and concentrated. The crude product wasfurther purified by column chromatography on a silica gel(hexane:ethyl acetate = 10:1) to provide trans-stilbene (85 mg,94%). All the products were identified by comparison oftheir spectroscopic data with authentic compounds.
87% With iron In methanol for 0.5h; Heating;

  • 26
  • [ 473-34-7 ]
  • [ 1754-62-7 ]
  • [ 141241-05-6 ]
YieldReaction ConditionsOperation in experiment
85% With 4 A molecular sieve; zinc(II) chloride In acetonitrile at 20℃; for 22h;
81% Stage #1: N,N-dichloro-p-toluenesulfonamide; Methyl cinnamate With [Pd(phen)Cl2] In acetonitrile at 20℃; for 22h; Stage #2: With sodium thiosulfate In water; acetonitrile
81% With 1-n-butyl-methylimidazolium tetrafluoroborate; 4 A molecular sieve; copper(I) triflate at 20℃; for 12h;
With copper acetylacetonate; 4 A molecular sieve In acetonitrile at 20℃; for 24h;
With zinc(II) chloride

  • 27
  • [ 103-26-4 ]
  • [ 130796-40-6 ]
YieldReaction ConditionsOperation in experiment
83% With potassium osmate(VI); sodium periodate; disodium hydrogenphosphate; dipotassium peroxodisulfate; methanesulfonamide; (9S,9"S)-9,9"-[phthalazine-1,4-diylbis-(oxy)]bis[10,11-dihydro-6'-methoxycinchonane] In water; <i>tert</i>-butyl alcohol at 20℃; enantioselective reaction; General procedure for the enantioselective dihydroxylation of olefins using (DHQD)2Phal General procedure: Water (5 mL/mmol substrate) was added to a solid mixture of K2S2O8 (1.5 equiv), Na2HPO4 (3 or 4 equiv), NaIO4 (0.2 equiv) or K3Fe(CN)6 (0.2 equiv), MeSO2NH2 (1 equiv) and K2OsO2(OH)4 (0.05 equiv) at room temperature, and the mixture was stirred for 5 min. (DHQD)2Phal (0.075 equiv), tert-BuOH (5 mL/mmol substrate), and the olefin (1 equiv) were then added sequentially, and the reaction was stirred at room temperature until olefin was consumed as judged by TLC. A solution of saturated aqueous Na2S2O3 was added, and the mixture was extracted with CH2Cl2 (3 x 5 mL/mmol substrate).The combined organic extracts were dried (Na2SO4), filtered, and concentrated under reduced pressure, and the crude product was purified by flash chromatography to provide the pure diol.
80% With AD-mix-α; methanesulfonamide In water; <i>tert</i>-butyl alcohol
  • 28
  • [ 292638-85-8 ]
  • [ 71-43-2 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
81% With ammonium peroxodisulphate; palladium diacetate; trifluoroacetic acid at 20℃; for 24h; Schlenk technique; Sealed tube;
65% With oxygen; anhydrous Sodium acetate; acetylacetone In propionic acid at 90℃; for 3h;
65% With 2-hydroxy-5-methyl-3-nitropyridine; palladium diacetate; 2-(6-hydroxy-3-oxo-3H-xanthene-9-yl) benzoic acid at 30 - 35℃; for 28h; Sealed tube; Irradiation; regioselective reaction;
65% With 2-hydroxy-5-methyl-3-nitropyridine; palladium diacetate; fluorescein at 30 - 35℃; Irradiation; regioselective reaction;
64% With tert-Butyl peroxybenzoate; 3,5-dichloropyridine; palladium diacetate; glacial acetic acid at 100℃; for 6h;
41% With ruthenium (III) chloride; carbon monoxide; oxygen at 180℃; for 48h;
3% 17 EXAMPLE 17 EXAMPLE 17 The reaction and post treatment were carried out in the same manner as described in Example 16 except that 60 ml of hexane was used instead of 60 ml of ethyl acetate, to obtain 0.108 g (0.67 millimole) of methyl cinnamate. The yield was 3% based on methyl acrylate and 640% based on the Rh atom.
16 EXAMPLE 16 The yield of methyl cinnamate was 6% based on methyl acrylate and 1170% based on the Rh atom.
With carbon monoxide In ethyl acetate at 220℃; for 6h; 16 EXAMPLE 16 EXAMPLE 16 Charged in an autoclave having an inner capacity of 200 ml, were 16.32 g (209 millimoles) of benzene, 1.745 g (20.26 millimoles) of methyl acrylate and 19.4 mg (0.026 millimole) of Rh4 (CO)12, followed by supply of 60 ml of ethyl acetate. Carbon monoxide under 30 kg/cm2 was introduced into the autoclave and reaction was carried out at 220° C. for 6 hours to obtain 0.197 g (1.22 millimoles) of methyl cinnamate.

  • 29
  • [ 103-26-4 ]
  • [ 90841-69-3 ]
YieldReaction ConditionsOperation in experiment
70% With potassium bromate; sulfuric acid; sodium hydrogensulfite In water; acetonitrile at 40℃; for 38h; a.i EXAMPLE (i) EXAMPLE (i) Synthesis of (+-)-methyl 2-bromo-3-hydroxy-3-phenylpropanoate of formula 2 where x=Br and R'=CH3 Potassium bromate (4 g, 24 mmol), was dissolved in 40 ml water and adjusted to pH 1-2 with 2M H2SO4. To the resultant solution was added methyl cinnamate (3 g, 20 mmol) in 40 ml acetonitrile. 1M sodium bisulphite solution (5.2 g in 50 ml) was added to the above mixture over a period of two hours with stirring and at 40° C. The reaction mixture was further stirred for 36 hrs till the reaction was complete (TLC monitored). The resulting solution was extracted with ethyl acetate (3*100 ml), and combined organic layer was washed with aqueous sodium sulphite followed by drying over anhydrous sodium sulphate. The contents concentrated in vacuo to give a crude material, which was purified by crystallization (benzene: hexane, 1:1) to furnish compound of formula 2 m.pt 63° C. (yield 70%). 1H-NMR (CDCl3) δ: 7.37(5H, s, Ar-H), 5.08(1H, d, J=8.25 Hz, CH-OH), 4.38(1H, d, J=8.24 Hz, CH-Br), 3.80(3H, s, COOCH3).
With N-Bromosuccinimide In water; acetonitrile at 25 - 30℃; for 8h; 4.1 General procedures for α-bromoketones and α-azidoketones from olefins General procedure: To a solution of the olefin (0.5-1.2mmol) in 10-16mL of acetonitrile-water (1:1) mixture was added NBS (1.05equiv) at rt. The reaction mixture was stirred until all the olefin was consumed, as monitored by TLC analysis. Subsequently, TetMe-IA (10mol%) and Oxone (1.0equiv) were introduced into the reaction mixture, and the stirring was continued. After completion of the oxidation as judged by TLC analysis, the reaction mixture was washed with saturated NaHCO3 solution. The organic matter was extracted 2-3 times with ethyl acetate or dichloromethane, and the combined organic extract was dried over anhyd Na2SO4. The solvent was removed in vacuo and the resultant residue was subjected to a short-pad silica gel column chromatography to isolate pure α-bromoketone.
  • 30
  • [ 369-57-3 ]
  • [ 292638-85-8 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
100% With palladium(II) acetate In water at 20℃; for 0.5h; Green chemistry; stereoselective reaction;
99% With 1-(2-hydroxyethyl)-3-methylimidazolium prolinate; palladium diacetate In neat (no solvent) at 20℃; for 0.5h; Green chemistry; General procedure for the Heck-Matsuda coupling General procedure: To a 50-mL round bottom ask, IL (2 mL), Pd(OAc)2 (3 mol %), olefin (1 mmol),and aryldiazonium tetrafluoroborate salt/aryldiazonium silica sulfate salt (1 mmol) was added and stirred at room temperature under aerobic conditions. After completion of the reaction [monitored by thin layer chromatography (TLC)], the reaction mixture was extracted with diethyl ether (2 * 20 mL) while the IL-Pd NPs remained the same in the reaction flask. The combined organic fractions were washed with water, dried over anhydrous sodium sulfate, and evaporated to obtain corresponding crude product. The crude product was puried by column chromatography with hexane/ethyl acetate (9:1) as eluent. Synthesized productswere confirmed from physical constant, IR, 1H, 13C NMR and mass analysis.
96% With Pd/Al2O3 In methanol at 25℃;
94% With Triton X 100 In water at 20℃; for 0.5h; Green chemistry; stereoselective reaction; General procedure for Matsuda-Heck Coupling In a 50 mL round-bottom flask, to a suspension of olefin (1 mmol) and Triton X 100 (5 mol %) in water (5 ml), benzenediazonium tetrafluoroborate salt (1.2 mmol) was added followed by addition catalyst (20 mg, 0.2 mol% Pd). The reaction mixture was stirred at room temperature for the time specified in Table 2 and progress was monitored by TLC. After the completion of reaction, the mixture was extracted with ethyl acetate (2 x 20 mL). The combined organic fractions were washed with water, dried over anhydrous sodium sulfate, and evaporated to obtain corresponding crude arylated product which was purified by column chromatography with hexane/ethyl acetate (9:1) as eluent.
91% With 11A-tobermorite; palladium diacetate In methanol chemoselective reaction;
90% Stage #1: benzenediazonium tetrafluoroborate; acrylic acid methyl ester With p-xylene-2-sulphonic acid sodium salt In water at 28℃; Stage #2: With palladium 10% on activated carbon In water for 1h; diastereoselective reaction;
68% In tetrahydrofuran at 20℃; for 3h;

  • 31
  • [ 103-26-4 ]
  • [ 71-43-2 ]
  • [ 3461-34-5 ]
YieldReaction ConditionsOperation in experiment
84% With oxygen; sodium acetate; acetylacetone In propionic acid at 90℃; for 3h;
67% With dipotassium peroxodisulfate; sodium acetate; palladium diacetate; acetic acid In acetonitrile at 80℃; for 24h;
  • 33
  • [ 103-26-4 ]
  • [ 109-73-9 ]
  • methyl 3-phenyl-3-(N-butylamino)propionate [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With lithium perchlorate at 20℃; for 2h;
43% With aluminum oxide In neat (no solvent) at 70℃; for 48h; Green chemistry; 3.2. Procedure for Preparation of Mono-Adducts General procedure: The amine (7.5 mmol) and the Michael acceptor (5 mmol) in a molar ratio of 1.5:1 were refluxedwith stirring in the presence of acidic alumina (1 g, 200 mol%). Heating was performed using an oilbath and the reaction was followed by TLC and GC until completion. The reaction was then allowedto cool down to room temperature and filtered through a filter paper. The catalyst was rinsed withethyl acetate/hexane and then concentrated by rotary evaporation. The crude reaction mixture waspurified using a silica-filled chromatographic column using hexane/ethyl acetate as eluents. Usually,for aliphatic amines, the mono-adduct was eluted using 7:3, 6:4 or 5:5 hexane/ethyl acetate whilstfor aromatic ones the solvent mixture used was 8:2 hexane/ethyl acetate. The yields of the purifiedproducts were recorded and then IR and NMR spectroscopy and MS spectrometry were performed.
  • 34
  • [ 925-90-6 ]
  • [ 103-26-4 ]
  • [ 2732-21-0 ]
YieldReaction ConditionsOperation in experiment
94% With copper(I) bromide dimethylsulfide complex In diethyl ether; dichloromethane at -75℃;
In various solvent(s) at -78℃;
98% ee With copper(I) bromide dimethylsulfide complex; (R)-1-[(Sp)-2-(dicyclohexylphosphanyl)ferrocenylethyl]diphenylphosphane In diethyl ether; dichloromethane at -70℃; for 16h; enantioselective reaction;
  • 35
  • [ 6627-55-0 ]
  • [ 103-26-4 ]
  • [ 16299-22-2 ]
YieldReaction ConditionsOperation in experiment
77% With N-Methyldicyclohexylamine; tetraethylammonium chloride In N,N-dimethyl acetamide at 95℃; for 48h;
77% With N-Methyldicyclohexylamine; tetraethylammonium chloride In ISOPROPYLAMIDE at 20 - 95℃; for 48h; 1 6-methyl-4-phenyl-chromen-2-one (I ; X+Z=0 ; W = CO) 2-Bromo-4-methylphenol (2.4 ml ; 19.7 MMOL), ET4NCI (2.2 g; 13.3 MOI), CY2 (Me) N (4.2 ml ; 19.7 MMOL) and Pd (OAC) 2 (59 mg; 0.26 MMOL) were added under nitrogen at room temperature to a solution of methyl cinnamate (2.1 g; 13.1 MMOL) in DIMETHYLACETAMIDE (40 ML). The reaction mixture was stirred at 959C for 48 h, then cooled and filtered on celite. The solution was diluted with Et20 and washed 3 times with H20. The organic phase was dried over NA2SO4 and the solvent was evaporated under vacuum. GC-MS showed a conversion of 94%. The raw reaction product was purified by flash chromatography. (SIO2, n-hexane: Et20 7: 3) and the fractions collected were crystallized from ET20/N-HEXANE to give pale yellow crystals (2.4 g; 77% yield).
  • 36
  • [ 1263311-99-4 ]
  • [ 103-26-4 ]
  • C31H30NO4P [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With potassium <i>tert</i>-butylate In tetrahydrofuran; dichloromethane at -7 - 20℃; Inert atmosphere; diastereoselective reaction; 4.2. General procedure General procedure: At -5 °C, under N2 and in a 20 mL flask containing 600 mg of (+/-)-1a (1.72 mmol, 1 equiv), are added successively 14 mL of dichloromethane, 200 μL of methyl methacrylate (1.89 mmol, 1.1 equiv), and 230 μL of a solution of t-BuOK in THF (0.6 M, 0.14 mmol, 0.08 equiv). Under stirring, the solution returned slowly to ambient temperature. A yellow tint appeared some minutes after addition of the base. At the end of the process two widely major compounds were obtained (δ 31P: 2.1a 50.33 and 2.1b 50.77 ppm) with a ratio of 37/63 and 26% de. After addition of water until reaching pH=7, extraction with dichloromethane, drying over Na2SO4, and evaporation of solvents under vacuum, a white solid was recovered. Further, purification by column chromatography on silica (hexane/ethyl acetate gradient: 70/30 to 0/100) gave a final white solid containing two diastereoisomers (580 mg, 75% yield).
  • 37
  • [ 292638-85-8 ]
  • [ 98-09-9 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
93% With {Pd[C6H2(CH2CH2NH2)-(OMe)(2),3,4] (μ-Br)}2; sodium acetate at 130℃; for 0.0666667h; Microwave irradiation; Ionic liquid;
90% With [Pd{C6H2-(CH2CH2NH2)-(OMe)2-3,4}Br(PPh3)]; potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 0.833333h; General procedure for Heck reactions of aryl halides with olefins General procedure: To a round-bottom flask equipped with a magnetic stirring bar were added monomeric palladacycle 2 (0.4 mol %), K2CO3 (1.1 mmol), olefin (2.2 mmol) and aryl halide (1 mmol) in NMP (3 mL). The mixture was heated at 130 °C using an oil bath and the progress was monitored by TLC (hexane/EtOAc, 80:20) and gas chromatography (GC). After completing the reaction, the mixture was diluted with n-hexane (30 mL) and H2O. The organic layer was washed with brine (20 mL), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by recrystallization from EtOH and H2O. The products were characterized by comparing their mp and IR, 1H and 13C NMR spectra with those reported in the literature.
  • 38
  • [ 2996-92-1 ]
  • [ 292638-85-8 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
76% With tetrabutyl ammonium fluoride; p-benzoquinone In tetrahydrofuran at 40℃; for 12h;
73% With C14H16N6; palladium diacetate; silver fluoride In N,N-dimethyl acetamide at 50℃; for 24h; 4.3. General procedure of palladium-catalyzed Mizoroki-Heck type reaction with aryl trialkoxysilanesCommentComment General procedure: To a mixture of olefin (0.5 mmol), AgF (0.191 mg, 1.5 mmol), Pd(OAc)2 (5.6 mg, 25 μmol), and ligand 1e (6.7 mg, 25 μmol) in DMAc (1.0 mL) was added aryl trialkoxysilane (1.0 mmol) at room temperature under an atmosphere of air. The mixture was stirred at 60 °C. After 24 h, the mixture was diluted with ethyl acetate and water. The organic layer was washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane or hexane/EtOAc=100 to 10/1).
67% With palladium diacetate; acetic anhydride; 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetic acid at 90℃; for 27h;
  • 39
  • [ 103-26-4 ]
  • [ 405-02-7 ]
  • [ 1198097-83-4 ]
YieldReaction ConditionsOperation in experiment
82% With palladium diacetate In methanol at 25℃; for 4h; 28 Synthesis of Methyl (E)-3-(3,4-dichlorophenyl)-3-phenylacrylate (7): To a solution of methyl cinnamate(1.6 g, 10 mmol) in methanol (60 mL), Pd(OAc)2(240 mg, 10 mol%) and 3,4-dichlorobenzenediazonium tetrafluoroborate(3.12 g, 12mmol) was added. The reaction mixture was stined at 25°C for 4 h. After completion of reaction (monitored by TLC), it was filtered through a pad of Celite and washed with methanol (3 x 15 mL). The combined filtrates were concentrated to give crude product, 7which upon column chromatographic purification with silica gel using petroleumether: ethyl acetate (3:7) as eluent gave pure 7 as colorless oil.Yield: 82%, colorless oil; IR (CHC13, cm’): Umax 699, 823, 874, 1190, 1275, 1549,1620, 1727, 2948; ‘H NMR (200 MHz, CDC13): ö 3.61 (s, 3H), 6.32 (s, 1H), 7.07-7.19(m, 3H), 7.37-7.41 (5H); ‘3C NMR (50 MHz, CDC13): ö 51.3, 118.1, 127.4, 128.1,128.7, 129.0, 130.0, 130.3, 132.9, 133.7, 137.7, 140.9, 154.3, 165.7; Anal. CalcdforC,6H,202C12 requires C, 62.56; H, 3.94; found C, 62.50; H, 3.95%.
82% With palladium diacetate In methanol for 4h; Reflux;
  • 40
  • 1-phenyl-3-methoxy-2-propyn-1-ol [ No CAS ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
95% With Fe3+-montmorillonite In methanol; 1,2-dichloro-ethane at 70℃; for 5h; 24 example 24 The 1-phenyl-3-methoxy-2-propyn-1-ol (162 mg, 1mmol) dissolved in 5mL1, in 2-dichloroethane, to join Fe3+-montmorillonite (100 mg) and methanol (5mmol, 0.2 ml), stirring and heating, in the 70 °C reaction under 5 hours, filtered to remove Fe3+-polynite, concentrated filtrate, product column chromatography separation to obtain a concentrate (E) - 3-phenyl-acrylic acid methyl ester 154 mg, yield 95%
  • 41
  • phenyldiazonium silica sulfate [ No CAS ]
  • [ 292638-85-8 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
99% With 1-(2-hydroxyethyl)-3-methylimidazolium prolinate; palladium diacetate In neat (no solvent) at 20℃; for 0.5h; Green chemistry; General procedure for the Heck-Matsuda coupling General procedure: To a 50-mL round bottom ask, IL (2 mL), Pd(OAc)2 (3 mol %), olefin (1 mmol),and aryldiazonium tetrafluoroborate salt/aryldiazonium silica sulfate salt (1 mmol) was added and stirred at room temperature under aerobic conditions. After completion of the reaction [monitored by thin layer chromatography (TLC)], the reaction mixture was extracted with diethyl ether (2 * 20 mL) while the IL-Pd NPs remained the same in the reaction flask. The combined organic fractions were washed with water, dried over anhydrous sodium sulfate, and evaporated to obtain corresponding crude product. The crude product was puried by column chromatography with hexane/ethyl acetate (9:1) as eluent. Synthesized productswere confirmed from physical constant, IR, 1H, 13C NMR and mass analysis.
  • 42
  • [ 67-56-1 ]
  • C24H19NO3 [ No CAS ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
99% With trimethylphosphane In dichloromethane; toluene at 20℃; for 1.5h; Alcoholysis of Imide 3 in Dichloromethane General procedure: To a 0.6 mL solution of α,β-unsaturated imide 3 (30 mg, 0.081 mmol) in CH2Cl2 was added the appropriate alcohol (0.162 mmol, 2.0 equiv) at r.t. Then 1.0 M Me3P in toluene (81 μL, 0.081 mmol, 1.0 equiv) was added slowly at r.t. After disappearance of the imide, the resulting mixture was concentrated under reduced pressure to remove CH2Cl2 and Me3P. The residue was purified by column chromatography (silicagel) to give ester 4. Methyl trans-Cinnamate (4a) Rf = 0.30 (n-hexane-EtOAc, 7:1); colorless solid; mp 33-35 °C. IR (ATR): 3068, 2990, 2944, 2846, 1711, 1636, 1494, 1452, 1438, 1314, 1198, 1164, 1012, 981, 934 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.70 (d, J = 16.0 Hz, 1 H), 7.55-7.50 (m,2 H), 7.41-7.37 (m, 3 H), 6.45 (d, J = 16.0 Hz, 1 H), 3.81 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 167.4, 144.8, 134.3, 130.3, 128.8, 128.0, 117.7, 51.7. HRMS (ESI): m/z [M + Na]+ calcd for C10H10O2Na: 185.0573; found: 185.0575.
  • 43
  • [ 67-56-1 ]
  • C24H19NO3 [ No CAS ]
  • [ 52481-82-0 ]
  • [ 103-26-4 ]
YieldReaction ConditionsOperation in experiment
1: 88% 2: 99% With trimethylphosphane In toluene at 20℃; for 3h; Alcoholysis of Imide 3 in Alcohol General procedure: To a solution of α,β-unsaturated imide 3 (30 mg, 0.081 mmol) in alcohol ROH (0.6 mL) was added 1.0 M Me3P in toluene (81 μL, 0.081 mmol, 1.0 equiv) slowly at r.t. After disappearance of the imide, the resulting mixture was concentrated under reduced pressure to remove the alcohol and Me3P. The residue was purified by column chromatography (silica gel) to give ester 4.
  • 44
  • [ 103-26-4 ]
  • [ 96857-55-5 ]
  • diethyl 1-fluoro-2-oxo-4-phenylbut-3-enylphosphonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.5h; 4.3 General procedure for the preparation of diethyl α-fluoro-β-ketophosphonates (6) General procedure: To solution of diethyl fluoromethylphosphonate 4 (187 mg, 1.10 mmol) and ester 5 (1.00 mmol) in THF (2.5 mL) was added dropwise 2.1 M LDA (1.0 mL, 2.10 mmol) at -78 °C. After complete addition, the reaction mixture was stirred at -78 °C for 0.5 h, then quenched with saturated aqueous NH4Cl (2 mL). The aqueous phase was extracted with EtOAc and the combined organic layers were washed with water and brine, then dried over Na2SO4, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel.
  • 45
  • 1-amino-3-bromo-5-methoxypyridin-1-ium 2,4,6-trimethylbenzene-1-sulfonate [ No CAS ]
  • [ 103-26-4 ]
  • methyl 6-bromo-4-methoxy-2-phenylpyrazolo[1,5-a]pyridine-3-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; N-ethyl-N,N-diisopropylamine In toluene at 0 - 80℃; for 3h; 17 Example 17 Synthesis of methyl 6-bromo-4-methoxy-2-phenylpyrazole[1,5-a]pyridine-3-carboxylate (W17) Add to the reaction tube at room temperature1-Amino-3-bromo-5-methoxypyridine 2,4,6-trimethylbenzenesulfonate (60.3mg, 0.15mmol),TEMPO (28.1mg, 0.18mmol), methyl cinnamate(48.7mg, 0.30mmol) and toluene (3.0mL),Add DIPEA (50.0μL, 0.30mmol) at 0,The reaction solution was stirred at 80°C for 3h,Concentrate the reaction solution under reduced pressure to obtain a crude product,The obtained crude product is purified by silica gel column chromatography (eluent is petroleum ether/ethyl acetate = 8:1) to obtain methyl6-Bromo-4-methoxy-2-phenylpyrazole[1,5-a]pyridine-3-carboxylate (45.5 mg, yield 84%).
84% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; N-ethyl-N,N-diisopropylamine In toluene at 0 - 80℃; for 4h; Inert atmosphere; regioselective reaction;
  • 46
  • [ 103-26-4 ]
  • [ 60456-13-5 ]
YieldReaction ConditionsOperation in experiment
87% With NBS; copper chloride (II) In methanol at 20℃; for 24h; regioselective reaction; methyl 2-bromo-3-methoxy-3-phenylpropanoate (2am) To a test tube were added methyl cinnamate (162.2 mg, 1 mmol), CuCl2 (3.4 mg, 2.5 mol%), N-iodosuccinimide (NBS) (178.0 mg, 1 mmol) and MeOH (2.0 mL). The mixture was stirred at room temperature for 24 h. Upon completion, the reaction mixture was transferred to a pear-shaped bottle, and evaporated to an appropriate amount. The residue was purified by chromatography on silica gel to afford the desired product 2am as yellow oil (237.6 mg, 87% yield);1H NMR (500 MHz, Chloroform-d) δ 7.41 - 7.32 (m, 5H), 4.56 (d, J = 9.9 Hz, 1H), 4.24 (d, J = 9.9 Hz, 1H), 3.83 (s, 3H), 3.21 (s, 3H). 13C NMR (500 MHz, Chloroform-d) δ 169.46, 136.85, 128.45, 128.10, 84.14, 57.63, 53.07, 47.08.
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