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[ CAS No. 4627-10-5 ] {[proInfo.proName]}

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Chemical Structure| 4627-10-5
Chemical Structure| 4627-10-5
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Product Details of [ 4627-10-5 ]

CAS No. :4627-10-5 MDL No. :MFCD00066915
Formula : C8H15BO2 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 154.01 Pubchem ID :-
Synonyms :

Safety of [ 4627-10-5 ]

Signal Word:Danger Class:3
Precautionary Statements:P210-P240-P241-P242-P243-P261-P264-P271-P280-P302+P352-P303+P361+P353-P304+P340-P305+P351+P338-P312-P332+P313-P337+P313-P362-P370+P378-P403+P233-P403+P235-P405-P501 UN#:1993
Hazard Statements:H225-H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 4627-10-5 ]

* 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 [ 4627-10-5 ]

[ 4627-10-5 ] Synthesis Path-Downstream   1~84

  • 1
  • [ 4627-10-5 ]
  • potassium vinyltrifluoroborate [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With potassium hydrogen bifluoride In methanol; water at 20℃;
  • 2
  • [ 1003-09-4 ]
  • [ 4627-10-5 ]
  • 4,4,6-Trimethyl-2-((E)-2-thiophen-2-yl-vinyl)-[1,3,2]dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With tributyl-amine; triphenylphosphine In toluene for 96h; Heating;
  • 3
  • [ 107-41-5 ]
  • [ 1826-67-1 ]
  • [ 4627-10-5 ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: vinyl magnesium bromide With Trimethyl borate In tetrahydrofuran at -78℃; for 1h; Stage #2: With hydrogenchloride In tetrahydrofuran; diethyl ether at 20℃; for 0.166667h; Stage #3: 2-methyl-2,4-pentanediol In tetrahydrofuran; diethyl ether at 20℃; for 1h;
71% Stage #1: vinyl magnesium bromide With Trimethyl borate In tetrahydrofuran at -78℃; Stage #2: With hydrogenchloride In tetrahydrofuran at 20℃; Stage #3: 2-methyl-2,4-pentanediol In diethyl ether
  • 4
  • [ 591-50-4 ]
  • [ 4627-10-5 ]
  • [ 60806-00-0 ]
YieldReaction ConditionsOperation in experiment
97% With tributyl-amine; triphenylphosphine In toluene for 8h; Heating;
With tributyl-amine; silver(I) acetate; triphenylphosphine In toluene at 110℃;
  • 5
  • [ 106-38-7 ]
  • [ 4627-10-5 ]
  • [ 622-97-9 ]
  • 4,4,6-trimethyl-2-(2-<i>p</i>-tolyl-vinyl)-[1,3,2]dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With tributyl-amine; triphenylphosphine In toluene for 96h; Heating;
  • 6
  • [ 624-31-7 ]
  • [ 4627-10-5 ]
  • 4,4,6-trimethyl-2-(2-<i>p</i>-tolyl-vinyl)-[1,3,2]dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With tributyl-amine; triphenylphosphine In toluene for 8h; Heating;
  • 7
  • [ 624-31-7 ]
  • [ 4627-10-5 ]
  • [ 622-97-9 ]
YieldReaction ConditionsOperation in experiment
83% With silver(l) oxide In tetrahydrofuran at 67℃; for 24h;
  • 8
  • [ 90-14-2 ]
  • [ 4627-10-5 ]
  • [ 826-74-4 ]
YieldReaction ConditionsOperation in experiment
96% With silver(l) oxide In tetrahydrofuran at 67℃; for 24h;
  • 9
  • [ 696-62-8 ]
  • [ 4627-10-5 ]
  • [ 637-69-4 ]
YieldReaction ConditionsOperation in experiment
90% With silver(l) oxide In tetrahydrofuran at 67℃; for 24h;
  • 10
  • [ 455-13-0 ]
  • [ 4627-10-5 ]
  • [ 402-50-6 ]
YieldReaction ConditionsOperation in experiment
76% With silver(l) oxide In tetrahydrofuran at 67℃; for 24h;
  • 11
  • [ 6214-23-9 ]
  • [ 4627-10-5 ]
  • [ 935464-58-7 ]
YieldReaction ConditionsOperation in experiment
54% With silver(I) acetate;palladium diacetate; tris-(o-tolyl)phosphine; In acetonitrile; Example 2 - Synthesis of Compounds 31 and 32 of the Present InventionIn order to access longer chain analogues of 16 and 17, i.e. similar to that of natural ATRA, the addition of a further alkene unit was required The preparation of the Z,Z- and E,E- dienyliodides 20 and 21 commenced therefore with the coupling of the two iodides 12 and 13 to 4,4,6-trimethyl-2-vinyl-l,3,2-dioxaborane using modified Heck-Mizoroki conditions developed in our group.(24, 30, 31) This led to the isolation of the two boronate species 18 and 19 in 58 and 90% yields, respectively, which after stereoselective iododeboronation(24, P T/GB2011/0016913532-37) provided either the Z- or ^-dienyliodides 20 and 21 in 59 and 78% yields, respectively (Scheme 4).(38)
  • 12
  • [ 6214-23-9 ]
  • [ 4627-10-5 ]
  • [ 935464-58-7 ]
  • [ 692-92-2 ]
  • 13
  • [ 6214-23-9 ]
  • [ 4627-10-5 ]
  • Z-hex-2-en-4-ynedioic acid dimethyl ester [ No CAS ]
  • 14
  • [ 6213-88-3 ]
  • [ 4627-10-5 ]
  • [ 935464-66-7 ]
YieldReaction ConditionsOperation in experiment
51% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine; In acetonitrile; at 50℃; for 48h;Schlenk technique; Inert atmosphere; Method 1: To a dry Schlenk flask was added Pd(OAc)2 (36 mg,0.16 mmol), P(o-tol)3 (0.10 g, 0.33 mmol) and AgOAc (0.601 g,3.60 mmol). The flask was purged with argon, and dry, degassed MeCN (10 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.655 mL, 3.80 mmol) was then added, followed by methyl (2E)-3-iodoprop-2-enoate (0.704 g, 3.32 mmol). The vessel was purged further with argon, and the reaction mixture was then heated to 50 C with vigorous stirring for 2 days. The mixture was allowed to cool, then diluted with Et2O (280 mL) and passed through a short Celite/silica plug. The organic extracts were washed with 5% HCl (40 mL), H2O (80 mL) and brine (80 mL), dried over MgSO4, filtered and evaporated to yield 0.98 g of crude product as an orange oil. The crude product was purified by silica gel chromatography, eluent 10% EtOAc in hexane elution. Pure fractions were evaporated to yield (2E,4E)-5-(4,4,6-trimethyl-[1,3,2-dioxaborinan-2-yl]-penta-2,4-dienoic acid methyl ester as a yellow oil (0.404 g, 51%). 1H NMR (400 MHz, CDCl3): delta 1.35-1.24 (9H, m), 1.5-1.47 (1H, m), 1.81 (1H, dd, J = 14.0, 2.9 Hz), 3.75 (3H, s), 4.24 (1H, dqd, J = 12.3, 6.2, 2.9 Hz), 5.99-5.86 (2H, m), 6.97 (1H, ddd, J = 17.3, 11.0, 0.7 Hz), 7.33-7.21 (1H, m); 11B NMR (128 MHz, CDCl3): delta 25.52; 13C NMR (101 MHz, CDCl3): delta 23.58, 28.62, 31.65, 46.41,52.12, 65.52, 71.67, 123.17, 143.89, 146.54, 167.93; IR (upsilonmax, cm-1) 2974.3 (w) 1719.5 (s) inter alia; LCMS (ESI) 239.2; HRMS (ESI) calculated [C12H19BO4H] 238.1470, found 238.1491. Method 2: To a dry flask was added methyl (2E)-3-iodoprop-2-enoate (2.82 g, 13.3 mmol), Pd(OAc)2 (0.150 g, 0.67 mmol), P(otol)3 (0.408 g, 1.34 mmol) and AgOAc (2.41 g, 14.4 mmol). The flask was purged with argon, and dry, degassed MeCN (80 mL) wasadded. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (2.6 mL,15 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was then heated to 50 C with vigorous stirring for 23h. The mixture was allowed to cool, then diluted with Et2O (200 mL) and passed through a short Celite/silicaplug. The organic extracts were washed with NH4Cl (200 mL), H2O(200 mL) and brine (200 mL), dried over MgSO4, filtered and evaporated to give crude product as a yellow oil (2.65 g, 83%). The compound was taken on to the next stage without any further purification or characterisation. Method 3: To a dry flask was added methyl (2E)- 3-iodoprop-2-enoate (2.82 g, 13.3 mmol), Pd(OAc)2 (0.15 g, 0.67 mmol), P(o-tol)3(0.408 g, 1.34 mmol) and AgOAc (2.41 g, 14.4 mmol). The flask was purged with argon, and dry, degassed MeCN (72 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (2.6 mL, 15 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was then heated to 30 C with vigorous stirring for 19 h. The mixture was allowed to cool, then diluted with Et2O (200 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give crude product as a yellow oil (2.84 g, 89%).The compound was taken on to the next stage without any further purification or characterisation. Method 4: To a dry flask was added methyl (2E)-3-iodoprop-2-enoate (1.0 g, 4.7 mmol), Pd(OAc)2 (0.011 g, 0.047 mmol), tri(2-furyl)phosphine (0.022 g, 0.094 mmol) and AgOAc (0.851 g, 5.11 mmol). The flask was purged with argon, and dry, degassed MeCN (28 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.93 mL, 5.4 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was stirred vigorously at room temperature for 3 days. The mixture was diluted with Et2O (71 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give crude product as a pale yellow oil (1.18 g, 99%). The compound was taken on to the next stage without any further purification or characterisation.
  • 15
  • [ 637-87-6 ]
  • [ 4627-10-5 ]
  • 4,4,6-trimethyl-2-[(E)-2-(4-chlorophenyl)ethenyl]-1,3,2-dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With tributyl-amine; silver(I) acetate; triphenylphosphine In toluene at 110℃; for 24h;
  • 16
  • [ 352-34-1 ]
  • [ 4627-10-5 ]
  • 4,4,6-trimethyl-2-[(E)-2-(4-fluorophenyl)ethenyl]-1,3,2-dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With tributyl-amine; silver(I) acetate; triphenylphosphine In toluene at 110℃; for 24h;
  • 17
  • [ 922-67-8 ]
  • [ 4627-10-5 ]
  • Z-hex-2-en-4-ynedioic acid dimethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
32% With copper(l) iodide; potassium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 50℃; for 5h;
  • 18
  • [ 191103-19-2 ]
  • [ 4627-10-5 ]
  • [ 191103-43-2 ]
YieldReaction ConditionsOperation in experiment
With sodium carbonate; 4-methylmorpholine N-oxide In 1,4-dioxane; water; toluene 16.F 4-(formyl)-2-phenylbenzoyl methionine methyl ester, alternate procedure EXAMPLE 16F 4-(formyl)-2-phenylbenzoyl methionine methyl ester, alternate procedure A mixture of (2-phenyl-4-bromobenzoyl) methionine methyl ester (100 mmol), 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane (100 mmol), tetrakis(triphenylphosphine)palladium (0) (3 mmol) in toluene and 2 M sodium carbonate in water (100 mL) is heated at 80° C. until the starting methyl ester disappears. The resulting mixture is extracted with ether, and washed with water, brine, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue is then purified by column chromatography on silica gel. To a solution of the resulting vinyl compound in dioxane/water (4/1) is added osmium tetraoxide (0.03 equivalent), N-methylmorpholine N-oxide (3 equivalents), and the reaction is stirred at 25° C. until TLC analysis shows the reaction to be complete. The reaction mixture is extracted with ether, which is washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue is then purified by column chromatography on silica gel to afford the title product.
  • 19
  • [ 1073534-83-4 ]
  • [ 4627-10-5 ]
  • [ 1073534-84-5 ]
YieldReaction ConditionsOperation in experiment
With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; Heating / reflux; To a solution of the compound 24 (0.89 g, 2.0 mMol) and tetrabutylammonium fluoride ( 10 ml, 1 M solution in tetrahydrofuran) was added 4,4,6-trimethyl-2-vinyl- 1,3,2-dioxaborinane (0.62 g, 4.0 mMol) and [l,l-bis(diphenylphosphino)- ferrocene]dichloropalladium(II) complex with dichloromethane (1 :1) (0.082 g, O.lmmol) at room temperature. Then the mixture was heated to reflux overnight. After quenching withed water, the mixture was extracted with EtOAc and concentrated to dryness, obtaining the crude product, which was purified by flash chromatography with Hexanes/EtOAc (4:1) to afford a pure compound 25 as a white solid in 48% yield. 25: 1H NMR (CD3OD) δ 7.98 (s, IH), 7.84 (m, 2H), 6.82 (m, 3H), 6.82 (m, IH), 6.70 (m, IH), 5.73 (m, IH), 5.25 (m, IH), 4.23 (m, 2H), 3.72 (t, J=5.4 Hz, 2H), 2.62 (m, 2H) ppm, m/z (M+l): 392.2.
  • 20
  • 6-N,N-dibenzoyl-2',5'-diethoxy-5'-vinyl-3'-O-tertbutyldimethylsilyl adenosine [ No CAS ]
  • [ 4627-10-5 ]
  • (E) 6-N,N-dibenzoyl-2',5'-diethoxy-6'-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)-5'-vinyl-3'-O-tertbutyldimethylsilyl adenosine [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% In dichloromethane (Ar); soln. of alkene and Hoveyda-Grubbs II catalyst in CH2Cl2 was poured into sealed tube, dioxaborinane was added at 40°C, stirred for 36 h; diluted with water and CH2Cl2, extd. with CH2Cl2, dried over Na2SO4, concd. in vac., column chromy. (silica gel, CH2Cl2/acetone 0-5%);
44% With Hoveyda-Grubbs catalyst second generation In dichloromethane at 40℃; for 41h; Inert atmosphere;
  • 21
  • [ 102294-59-7 ]
  • [ 102-82-9 ]
  • [ 1206775-11-2 ]
  • [ 6163-58-2 ]
  • [ 4627-10-5 ]
  • [ 1206772-62-4 ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; ammonium hydroxide; sodium tetrahydroborate; diisobutylaluminium hydride; sodium carbonate In methanol; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; ethyl acetate; toluene 46.162 N-(4-{(E)-2-[3-(1-Hydroxymethyl-cyclopropyl)-5-(2-oxo-1,2-dihydro-pyridin-3-yl)-phenyl]-vinyl}-phenyl)-methanesulfonamide (I-162) N-{4-[(E)-2-(4,4,6-Trimethyl-[1,3,2]dioxaborinan-2-yl)-vinyl]-phenyl}-methanesulfonamide (242) To a solution of Pd(OAc)2 (0.076 g), tris-(ortho-tolyl)-phosphine (0.246 g, 1 mmol) and toluene (16 mL) were added sequentially N-(4-iodo-phenyl)-methanesulfonamide (2.00 g, 7 mmol, CASRN 102294-59-7), tributyl amine (1.92 mL) and 4,4,6-trimethyl-2-vinyl-[1,3,2]dioxaborinane (1.244 g, 8 mmol, CASRN 4627-10-5). The reaction was heated at reflux for 72 h, cooled to RT and partitioned between Et2O (100 mL) and 1M HCl (20 mL). The aqueous layer was withdrawn and re-extracted with Et2O. The organic phases were washed sequentially with H2O and brine. The extracts were combined, dried (Na2SO4), filtered and evaporated. The residue was purified by SiO2 chromatography eluding with an EtOAc/hexane gradient (0 to 30% EtOAc) to afford 1.4 g (58%) of 242. step 1-To a solution of 238a (0.180 g, 0.598 mmol) in DCM 8 mL) cooled to -78° C. was added a solution of DIBAL and toluene (0.9 mL, 0.897 mmol, 1.0 M solution in toluene) and the resulting solution stirred at -78° C. for 2 h. The reaction was quenched with 2 N HCl and extracted with DCM. The combined extracts were washed with sat'd. NaHCO3, dried (Na2SO4), filtered and evaporated. The crude product was purified by SiO2 chromatography eluding with a EtOAc/hexane gradient (0 to 10% EtOAc) to afford 0.13 g (71.5%) of 238b. step 2-Suzuki coupling of 238b and 213 was carried out in accord with the procedure in step 4 of example 38 to afford 240. The product was purified by chromatography eluding with a solution contain 50% DCM and 50% of a mixture of DCM/MeOH/NH4OH (10:10:1) to afford 240. step 3-A tube was charged with 240 (0.08 g, 0.251 mmol), 242 (0.097 g, 0.30 mmol), Na2CO3 (0.08 mmol, 0.754 mmol), Pd(PPh3)4 (0.03 g, 0.026 mmol), DCM (1 mL) and MeOH (3 mL), sealed and irradiated in a microwave synthesizer at 115° C. for 40 min. The solution was filtered and concentrated in vacuo. The crude product was purified by SiO2 chromatography eluding with a solution contain 50% DCM and 50% of a mixture of DCM/MeOH/NH4OH (10:10:1) to afford 60 mg 244. step 4-To a solution of 244 (0.060 g, 0.138 mmol) and MeOH (3 mL) cooled to 0° C. was added NaBH4 (0.026 g, 0.69 mmol). After 1 h the reaction was quenched with sat'd. NH4Cl and the resulting solution concentrated in vacuo. The crude product was purified by SiO2 chromatography eluding with a solution contain 50% DCM and 50% of a mixture of DCM/MeOH/NH4OH (10:10:1) to afford 40 mg of I-162 as a white powder.
  • 22
  • [ 1178884-85-9 ]
  • [ 4627-10-5 ]
  • [ 1202932-32-8 ]
YieldReaction ConditionsOperation in experiment
79% With potassium <i>tert</i>-butylate In tetrahydrofuran for 2.5h; sealed vial; Heating; Microwave; 11 Example 11 The lactam (1 g, 2.9 mmol), vinylboronic acid 2-methyl-2,4-prentanediol ester (560 mg, 1.2 equiv), tetrakistriphenylphosphine palladium (168 mg, 0.05 equiv), and KOtBu (410 mg, 1.2 equiv) in THF (19 mL) were heated a sealed vial for 150 minutes in a microwave reactor. The mixture was concentrated under reduced pressure, and the residue was purified by flash column chromatography on silica gel to provide the desired product (469 mg, 79%).
  • 23
  • [ 3376-26-9 ]
  • [ 4627-10-5 ]
  • [ 162365-58-4 ]
YieldReaction ConditionsOperation in experiment
77% Stage #1: N-Benzylidenebenzylamine N-oxide; 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane With dimethyl zinc(II) In toluene at 40℃; for 16h; Inert atmosphere; Stage #2: With water; ammonium chloride at 20℃; chemoselective reaction;
  • 24
  • [ 102294-59-7 ]
  • [ 4627-10-5 ]
  • [ 1206775-11-2 ]
YieldReaction ConditionsOperation in experiment
58% With tributyl-amine In toluene for 72h; Inert atmosphere; Reflux; 9 To a solution of Pd(OAc)2 (0.076 g) and tm-(or^o-tolyl)-phosphine (0.246 g, 1 mmol) and toluene (16 mL) were added sequentially N-(4-iodo-phenyl)-methanesulfonamide (2.00 g, 7 mmol, CASRN 102294-59-7), tributyl amine (1.92 mL) and 4,4,6-trimethyl-2-vinyl- [l,3,2]dioxaborinane (1.244 g, 8 mmol) and the reaction was heated at reflux for 72 h. The reaction was cooled to RT and partitioned between Et2O (100 mL) and IM HCl (20 mL). The aqueous layer was withdrawn and re-extracted with Et2O. The organic phases were washed sequentially with H2O and brine. The extracts were combined, dried (Na2SO4), filtered and evaporated. The residue was purified by SiO2 chromatography eluting with an EtOAc/hexane gradient (0 to 30% EtOAc) to afford 1.4 g (58%) of (89).
58% With tributyl-amine; tris-(o-tolyl)phosphine In toluene for 72h; Reflux; 7 To a solution of Pd(OAc)2 (0.076 g), tris-(ortho-tolyl)-phosphine (0.246 g, 1 mmol) and toluene (16 mL) were added sequentially N-(4-iodo-phenyl)-methanesulfonamide (2.00 g, 7 mmol, CASRN 102294-59-7), tributyl amine (1.92 mL) and 4,4,6-trimethyl-2-vinyl-[1,3,2]dioxaborinane (1.244 g, 8 mmol, CASRN 4627-10-5). The reaction was heated at reflux for 72 h, cooled to RT and partitioned between Et2O (100 mL) and 1M HCl (20 mL). The aqueous layer was withdrawn and re-extracted with Et2O. The organic phases were washed sequentially with H2O and brine. The extracts were combined, dried (Na2SO4), filtered and evaporated. The residue was purified by SiO2 chromatography eluting with an EtOAc/hexane gradient (0 to 30% EtOAc) to afford 1.4 g (58%) of 39.
  • 25
  • [ 1287212-33-2 ]
  • [ 4627-10-5 ]
  • [ 1287212-36-5 ]
YieldReaction ConditionsOperation in experiment
87% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 48h; Inert atmosphere;
  • 26
  • [ 610-97-9 ]
  • [ 4627-10-5 ]
  • [ 1287212-32-1 ]
YieldReaction ConditionsOperation in experiment
84% With silver(I) acetate; palladium diacetate; triphenylphosphine In acetonitrile at 70℃; for 2h; Inert atmosphere;
  • 27
  • [ 1247001-60-0 ]
  • [ 4627-10-5 ]
  • [ 1247001-59-7 ]
YieldReaction ConditionsOperation in experiment
88% Stage #1: N-benzyl-6-bromo-1H-indazole With sodium hydroxide In tetrahydrofuran; water for 0.166667h; Inert atmosphere; Stage #2: 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane In tetrahydrofuran; water at 65℃; for 24h; Inert atmosphere; 2 Synthesis of Nl-Benzyl-6-vinyl-lH-indazole[00145] Method 1 : A mixture of Nl-Benzyl-6-bromo-lH-indazole (10.2 g, 35.5 mmol) and NaOH (4.3 g, 107 mmol) in THF/water (9:1, 350 mL) was purged with nitrogen. In a separate flask, Pd(OAc)2 (0.16 g, 0.7 mmol, 2 mol%) and PPh3 (0.37 g, 1.4 mmol, 4 mol%) were stirred together in nitrogen-purged dry THF (35 mL) for 10 min, forming a red solution with some suspended solids. Vinylboronic acid pinacol ester (7.5 mL, 44.4 mmol) and the catalyst solution were added to the reaction mixture, and the resulting solution purged once more with nitrogen. The mixture was warmed in an oil bath set to 65 °C; TLC indicated consumption of starting material within 7 h. The mixture was concentrated under reduced pressure to remove most of the THF, then diluted with water (50 mL), brine (50 mL) and EtOAc (250 mL). The layers were separated and the aqueous phase extracted with further EtOAc (4 x 50 mL). The combined organic portions were washed with brine, dried over Na2S04, filtered and concentrated (at 70 °C/20 mbar) to afford the crude product. This was chromatographed on silica using 10-20% EtOAc in cyclohexane to afford the title compound (7.5 g, 90%) as a yellow oil that solidified on standing. NMR (400 MHz, CDC13) δ 7.98 (s, 1 H), 7.63 (d, J = 8.4 Hz, 1 H), 7.29 - 7.19 (m, 5H), 7.18 - 7.13 (m, J = 7.0 Hz, , 2H), 6.75 (dd, J = 17.6, 10.9 Hz, 1 H), 5.76 (d, J = 17.5 Hz, 1H), 5.53 (s, 2H), 5.26 (d, J = 10.9 Hz, 1H). MS (ES+): 235 ([M+H]+); calcd for [C16H14N2+ H]+ 235.1.
  • 28
  • methyl (Z)-3-iodo-2-butenoate [ No CAS ]
  • [ 4627-10-5 ]
  • [ 1381755-77-6 ]
YieldReaction ConditionsOperation in experiment
78% With silver(I) acetate In acetonitrile 2 Methyl tetrolate 22 was treated with sodium iodide and acetic acid to yield Z-3-iodoalkene 23 as a single stereoisomer in 89% yield.(39, 40) Subsequent treatment with iodic acid in benzene for 20 hours resulted in equilibration to give a readily separable 1 :1 mixture of stereoisomers 23 and 24. Attempts to increase the yield of the trans stereoisomer 24 through increased reaction times provided a yield of 66% after 48 hours, with no further improvement in yield seen for longer reaction periods. Each stereoisomer 23 and 24 were then coupled with the vinylboronate ester (Scheme 5) to give the (2Z,4£)- and (2£',4£)-dienylboronates 25 and 26 in 78 and 74% yields, respectively. Subsequent iododeboronation provided corresponding Z,E- and i^-dienyliodides 27 and 28 in 98 and 86% yields, respectively.
  • 29
  • methyl (2E,4E)-5-iodod-3-methylpenta-2,4-dienoate [ No CAS ]
  • [ 4627-10-5 ]
  • [ 1381755-88-9 ]
YieldReaction ConditionsOperation in experiment
67% With silver(I) acetate In acetonitrile 4 To complete the series of synthetic retinoids, a longer polyene derivative was prepared using a similar approach, i.e. as outlined in Scheme 10. Hence, dienyliodide 28 was coupled with 4,4,6-trimethyl-2-vinyl-l,3,2-dioxaborane to generate the trienylboronate 39 in a 67% yield and iododeboronation gave trienyliodide 40 in a 65% yield. Coupling of 40 to acetylene 7 yielded the trienyne methyl ester 41 in 64% yield as a stable mixture of isomers. Subsequent saponification of the ester 41 gave the free acid 42 in an 87% yield. However, it was isolated as a mixture of the two stereoisomers confirmed by NMR in a ratio of 1 :0.4 (Scheme 10). Due to the highly sensitive nature of the compound it was assumed that a single isomer was probably unattainable as isomerisation occurs under general laboratory light. Consequently, isomerisation occurs at all stages of the synthesis including in the reaction mixtures and work up procedures. Therefore, the mixture of the two inseparable stereoisomers 42 and 43 was examined for biological activity without further attempts at separation.
67% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 22h; Schlenk technique; Inert atmosphere; stereoselective reaction;
  • 30
  • [ 1027804-05-2 ]
  • [ 4627-10-5 ]
  • [ 1403890-92-5 ]
YieldReaction ConditionsOperation in experiment
64% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide; acetonitrile at 50℃; for 60h; stereoselective reaction;
  • 31
  • [ 184370-56-7 ]
  • [ 4627-10-5 ]
  • [ 1403890-94-7 ]
YieldReaction ConditionsOperation in experiment
58% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide; acetonitrile at 50℃; for 17h; stereoselective reaction;
  • 32
  • [ 371172-65-5 ]
  • [ 4627-10-5 ]
  • [ 1403890-93-6 ]
YieldReaction ConditionsOperation in experiment
80% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide; acetonitrile at 50℃; for 17h; stereoselective reaction;
  • 33
  • 5-bromo-2-chloro-3-fluoro-pyridine [ No CAS ]
  • [ 4627-10-5 ]
  • [ 1416788-10-7 ]
YieldReaction ConditionsOperation in experiment
85% With tetrabutyl ammonium fluoride; potassium carbonate In tetrahydrofuran at 60℃; for 16h; sealed bottle; 4 To a solution of 101 (5.00g, 23.8 mmol) and 4,4,6-trimethyl-2-vinyl-l ,3,2-dioxaborinane (1 1 1 , 3.29 g, 21.39 mmol, Sigma- Aldrich) in a mixture of TBAF (30.0 mL) and THF (64.0 mL) under an argon atmosphere was added bis(triphenylphosphine)dichloropalladium(II) catalyst (Pd(PPh3)2Cl2, 1.33 g, 1.90 mmol, Sigma-Aldrich) and K2C03 (8.20 g, 59.4 mmol). The resulting reaction mixture was heated to 60°C and held for 16 hrs in a sealed bottle. The mixture was cooled to a temperature of about 25°C, diluted with water, and extracted with EtOAc. The organic layer was separated, washed with brine, and concentrated. The residue was chromatographed on a silica gel column eluted with EtOAc:hexanes to provide 3.2 g of 1 12 as a colorless oil (85% yield). NMR (CDC13) δ: 5.48 (1 H, d, J=10.97Hz), 5.83 (1H, d, J=17.62Hz), 6.68 (1H, dd, J=10.97, 17.62Hz), 7.52 (1H, d, J=1.60Hz), 8.20 (1H, d, J=1.60Hz). LC/MS (M+1): m/z = 5S.
  • 34
  • [ 1256790-78-9 ]
  • [ 4627-10-5 ]
  • 3-chloro-5-cyano-2-vinylpyridine [ No CAS ]
YieldReaction ConditionsOperation in experiment
58% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 13h; Inert atmosphere;
58% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 13h; Inert atmosphere;
  • 35
  • [ 35588-79-5 ]
  • [ 4627-10-5 ]
  • [ 1381755-78-7 ]
YieldReaction ConditionsOperation in experiment
74% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 55℃; for 22h; Schlenk technique; Inert atmosphere; stereoselective reaction;
  • 37
  • 3-[4-bromobenzyl]-8-oxa-3-azabicyclo[3.2.1]octane [ No CAS ]
  • [ 4627-10-5 ]
  • (E)-3-(4-(2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)vinyl)benzyl)-8-oxa-3-azabicyclo[3.2.1]octane [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With bis(tri-t-butylphosphine)palladium(0); triethylamine In toluene at 20 - 80℃; Inert atmosphere;
  • 38
  • C20H21NO3Si [ No CAS ]
  • [ 4627-10-5 ]
  • C26H32BNO5Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 4h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 39
  • C17H24OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C23H35BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 40
  • C16H22OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C22H33BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 4.5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 41
  • C16H22O2Si [ No CAS ]
  • [ 4627-10-5 ]
  • C22H33BO4Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 3h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 42
  • C15H19FOSi [ No CAS ]
  • [ 4627-10-5 ]
  • C21H30BFO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 3h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 43
  • C17H22O2Si [ No CAS ]
  • [ 4627-10-5 ]
  • C23H33BO4Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 4.5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 44
  • C16H22OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C22H33BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 3h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 45
  • dimethyl-(1-methyl-4-phenyl-but-3-ynyloxy)-vinyl-silane [ No CAS ]
  • [ 4627-10-5 ]
  • C21H31BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 3.5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 46
  • C21H32OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C27H43BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 3h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 47
  • [ 4627-10-5 ]
  • C14H26B2O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
43% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In 1,2-dichloro-ethane at 85℃; Schlenk technique; Inert atmosphere;
With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II); Triethoxyvinylsilane In toluene at 80℃; for 24h; Schlenk technique; Inert atmosphere;
  • 48
  • C22H26OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C28H37BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
58% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 6h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 49
  • C19H26OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C25H37BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 6h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 50
  • C21H24OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C27H35BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 2h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 51
  • C20H22OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C26H33BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
54% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 5.5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 52
  • C20H22OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C26H33BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
63% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 4h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 53
  • C26H26OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C32H37BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 3.5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 54
  • C20H28OSi [ No CAS ]
  • [ 4627-10-5 ]
  • C26H39BO3Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 85℃; for 4.5h; Inert atmosphere; Schlenk technique; stereoselective reaction;
  • 55
  • methyl (S)-3-(6-bromo-4-((3-ethoxy-1-ethyl-1H-pyrazol-4-yl)sulfonyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate [ No CAS ]
  • [ 4627-10-5 ]
  • methyl 3-((2S)-4-((3-ethoxy-1-ethyl-1H-pyrazol-4-yl)sulfonyl)-6-((E)-2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)vinyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With tris-(dibenzylideneacetone)dipalladium(0); triethylamine In toluene at 80℃; for 24h; 87.II Synthesis of Methyl 3-((2S)-4-((3-ethoxy-1-ethyl-1H-pyrazol-4-yl)sulfonyl)-6- ((E)-2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)vinyl)-3,4-dihydro-2H- benzo[b][1,4]oxazin-2-yl)propanoate A mixture o met y - - - romo- - -et oxy- -ethyl-1H-pyrazol-4- yl)sulfonyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate (500 mg, 1.00 mmol), 4,4,6- trimethyl-2-vinyl-1,3,2-dioxaborinane (184.8 mg, 1.20 mmol), bis(tri-tert- butylphosphine)palladium(0) (51.1 mg, 0.10 mmol), triethylamine (8 mL), and toluene (15 mL) was stirred for 24 hours at 80 °C. The pH value of the solution was adjusted to 3-4 with 2 M HCl. The resulting solution was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried (Na2SO4) and concentrated. The resulting residue was purified via MPLC eluting with a gradient of 10-20% ethyl acetate in petroleum ether to afford methyl 3-((2S)-4-((3-ethoxy-1-ethyl-1H-pyrazol-4-yl)sulfonyl)-6-((E)-2-(4,4,6- trimethyl-1,3,2-dioxaborinan-2-yl)vinyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate (480 mg, 84%) as a yellow oil.
  • 56
  • (S)-methyl 3-(6-bromo-4-((3-(trifluoromethyl)phenyl)sulfonyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate [ No CAS ]
  • [ 4627-10-5 ]
  • methyl 3-((2S)-4-((3-(trifluoromethyl)phenyl)sulfonyl)-6-((E)-2-(4,4,5-trimethyl-1,3,2-dioxaborinan-2-yl)vinyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82.7% With bis[tris( 1,1-dimethylethyl)phosphine]-palladium; triethylamine In toluene at 80℃; Inert atmosphere; 14.I Part I -- Synthesis of methyl 3-((2S)-4-((3-(trifluoromethyl)phenyl)sulfonyl)-6-((E)-2- (4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)vinyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2- yl)propanoate [000376] A mixture of (S)-methyl 3-(6-bromo-4-((3-(trifluoromethyl)phenyl)sulfonyl)- 3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate (15.35 g, 30.2 mmol), triethylamine (6.11 g, 60.4 mmol), and 4,4,5-trimethyl-2-vinyl-1,3,2-dioxaborinane (6.20 g, 36.2 mmol) in toluene (300 mL) was degassed and was placed under an atomosphere of nitrogen. Bis-(tri-tert- butyl)phosphine palladium (0.77 g, 1.51 mmol) was added and the reaction was heated to 80°C overnight. Then, the mixture was cooled and subsequently partitioned between ethyl acetate and water. The organic layer was dried (Na2SO4), and concentrated onto a small amount of silica gel. The residue was purified by MPLC eluting with a gradient of ethyl acetate in hexanes. The fractions containing the major UV active component were concentrated to afford methyl 3-((2S)-4-((3-(trifluoromethyl)phenyl)sulfonyl)-6-((E)-2-(4,4,6-trimethyl-1,3,2- dioxaborinan-2-yl)vinyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-yl)propanoate (14.52 g, 82.7%) as a thick amber oil.1H-NMR (400 MHz, DMSO-d6) δ ^ ^ ^ ^ ^ ^ ^d, 1H), 7.93 (m, 2H), 7.81 (t, 1H), 7.72 (s, 1H), 7.27 (d, 1H), 7.08 (d, 1H), 6.76 (d, 1H), 5.83 (d, 1H), 4.33 (d, 1H), 4.25 (m, 1H), 3.54 (s, 3H), 3.39 (m, 2H), 2.39 (m, 2H), 1.90 (m, 2H), 1.73 (m, 1H), 1.45 (m, 1H), 1.27 (s, 6H), 1.22 (d, 3H).
  • 57
  • [ 893566-74-0 ]
  • [ 4627-10-5 ]
  • tert-butyl 6-vinyl-3,4-dihydroisoquinoline-2(1H)-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium <i>tert</i>-butylate; triphenylphosphine In tetrahydrofuran at 67℃; for 24h; 84.A Step A. lert-butyl 6-vinyl -3,4-dihvdroisoquinoline-2(1 H)-carboxvlate To a stirred solution of tert-butyi 6-bromo-3,4-dihydroisoquinoline-2( 1H)-carboxyiate (1.5 g, 4.80 mrnol) in TI-IF (30 mL) was added 4,4,6-trimethyl-2-vinyl-i,3,2-dioxahorinane (0.740 g. 4.80 mmol), triphenylphosphine (1.260 g, 4.80 rnmol) and potassium 2-methyl- propan-2-olate (0.027 g, 0.240 mmol). The mixture was stirred at 67°C for 24 h, The mixture was washed with water (2 x10 inL) and extracted with EtOAc (2 x30 inL). The extract was dried over by Na2SO4 filtered,and concentrated in vacuo. The residue was purified by silica gel coiunm chromatography(PE:EtOAc=20 :1) to give the title compound.
  • 58
  • 1-bromo-4-[(E)-2-iodoethenyl]-2-methoxybenzene [ No CAS ]
  • [ 4627-10-5 ]
  • 2-[(1E,3E)-4-(4-bromo-3-methoxyphenyl)buta-1,3-dien-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With dichlorobis(tri-O-tolylphosphine)palladium; silver(I) acetate; palladium diacetate In acetonitrile at 50℃; for 18h; Inert atmosphere;
  • 59
  • {3-[7-chloro-4-(morpholin-4-yl)pyrido[3,2-d]pyrimidin-2-yl]phenyl}methanol [ No CAS ]
  • [ 4627-10-5 ]
  • (3-(4-morpholino-7-vinylpyrido[3,2-d]pyrimidin-2-yl)phenyl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene at 150℃; for 1h; Microwave irradiation; Inert atmosphere; A.5.1 (3-(4-Morpholino-7-vinylpyrido[3,2-d]pyrimidin-2-yl)phenyl)methanol (17) General procedure C: Under an argon atmosphere, in a 5 mL vial, 1.0 equiv. of 2-Chloro-4-(N-R1, R2)pyrido[3,2-d]pyrimidine (8 or 10) was dissolved in a mixture (toluene/ethanol, 2/1). 2.0 equiv. of potassium carbonate, 1.2 equiv. of boronic acid were added into the medium as well as 0.05 equiv. of tetrakis(triphenylphosphino) palladium(0). The mixture was irradiated with microwaves at 150° C. for one hour. After concentration under reduced pressure, the residue was taken up in ethyl acetate (25 mL) and washed with water (10 mL). The organic extracts were dried on MgSO4, filtered and then concentrated under reduced pressure. The reaction crude was then purified by a chromatography column. The compound (17) was synthesized from the compound (8) (210 mg, 0.59 mmol) by following the general procedure C and then purified by chromatography column on silica gel under pressure (AcOEt/EP, 2/8) in order to obtain a yellow 49 solid with a yield of 85%. MP: 160° C.; Infrared (Diamand ATR, cm-1) ν: 3293, 2922, 1488, 1440, 1308, 1109, 1069, 973; 1H NMR (400 MHz, CDCl3) δ: 3.92-3.95 (m, 4H, 2×CH2(O)), 4.60 (bs, 4H, 2×CH2(N)), 4.81 (s, 2H, CH2), 5.58 (d, 1H, J=11.0 Hz, Halkene), 6.06 (d, 1H, J=17.6 Hz, Halkene), 6.86 (dd, 1H, J=11.0 Hz, J=17.6 Hz, Halkene), 7.48-7.50 (m, 2H, 2×Harom), 8.12 (d, 1H, J=2.1 Hz, H8), 8.41-8.43 (m, 1H, Harom), 8.48 (s, 1H, Harom), 8.74 (d, 1H, J=2.1 Hz, H6); 13C NMR (101 MHz, CDCl3) δ: 48.1 (2×CH2), 65.4 (CH2), 67.3 (2×CH2), 119.0 (CH2), 127.0 (CH), 127.9 (CH), 128.6 (CH), 129.2 (CH), 132.1 (CH), 132.9 (CH), 136.2 (Cq), 138.4 (Cq), 141.1 (Cq), 144.8 (CH), 148.0 (Cq), 159.1 (Cq), 160.1 (Cq), 167.5 (Cq); HRMS (EI-MS): C20H20N4O2[M+H]+, calculated m/z 349.1659. found m/z 349.1661.
  • 60
  • 4-(7-chloro-2-(3-(methoxymethoxy)phenyl)pyrido[3,2-d]pyrimidin-4-yl)morpholine [ No CAS ]
  • [ 4627-10-5 ]
  • 4-(2-(3-(methoxymethoxy)phenyl)-7-vinylpyrido[3,2-d]pyrimidin-4-yl)morpholine [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene at 150℃; for 1h; Microwave irradiation; Inert atmosphere; A.5.1 4-(2-(3-(methoxymethoxy)phenyl)-7-vinylpyrido[3,2-d]pyrimidin-4-yl)morpholine (13) General procedure: General procedure B: Under an argon atmosphere, in a 5 mL vial, 1.0 equiv. of 2-Chloro-4-(N-R1R2)pyrido[3,2-d]pyrimidine (11 or 12) was dissolved in a mixture (toluene/ethanol, 2/1). 2.0 equiv. of potassium carbonate, 1.2 equiv. of boronic acid were added into the medium as well as 0.05 equiv. of tetrakis(triphenylphosphino) palladium(0). The mixture was irradiated with microwaves at 150° C. for one hour. After concentration under reduced pressure, the residue was taken up in ethyl acetate (25 mL) and washed with water (10 mL). The organic extracts were dried on MgSO4, filtered and then concentrated under reduced pressure. The reaction crude was then purified by a chromatography column. Deprotection step: In a 25 mL flask, 1.0 equiv. of a compound protected with a methoxymethoxy group (13 and 15) was dissolved in dioxane (10 mL). 6 equiv. of a hydrochloric gas solution (4 M in dioxane) were injected into the medium. The mixture was left with stirring at room temperature for one to three hours. The precipitate was washed with petroleum ether and then recovered by filtration in order to obtain the final product without any additional purification.The compound (13) was synthesized from (26 11) (250 mg, 0.65 mmol) by following the general procedure B and then purified by chromatography column on silica gel under pressure (AcOEt/EP, 2/8) in order to obtain a yellow 41 solid with a yield of 91%. MP: 105° C.; Infrared (Diamand ATR, cm-1) ν: 2856, 1527, 1487, 1454, 1343, 1275, 1111, 1070, 1021, 956, 910, 739; 1H NMR (400 MHz, CDCl3) δ: 3.52 (s, 3H, CH3), 3.96-3.89 (m, 4H, 2×CH2(O)), 4.58 (bs, 4H, 2×CH2(N)), 5.28 (s, 2H, CH2), 5.56 (d, 1H, J=11.0 Hz, CH2alkene)) 6.05 (d, 1H, J=17.7 Hz, CH2alkene), 6.84 (dd, 1H, J=11.0 Hz, J=17.7 Hz, CHalkene), 7.20-7.13 (m, 1H, Harom), 7.40 (t, 1H, J=7.9 Hz, Harom), 8.19-8.09 (m, 3H, 2×Harom and H8), 8.72 (d, 1H, J=1.9 Hz, H6); 13C NMR (101 MHz, CDCl3) δ: 48.3 (2×CH2), 56.3 (CH3), 67.5 (2×CH2), 94.7 (CH2), 116.5 (CH), 118.4 (CH), 119.0 (CH2), 122.3 (CH), 129.5 (CH), 132.5 (Cq), 132.6 (CH), 133.2 (CH), 136.2 (Cq), 140.2 (Cq), 144.9 (CH), 148.4 (Cq), 157.6 (Cq), 159.4 (Cq), 160.2 (Cq); HRMS (EI-MS): C21H22N4O3 [M+H]+, calculated m/z 379.1765. found m/z 379.1766.
91% With potassium carbonate In ethanol; toluene at 150℃; for 1h; Microwave irradiation; General procedure B: General procedure: A solution of halogenated derivative (1.0 eq.), potassium carbonate(3.0 eq.), 4.4.6-trimethyl-2-vinyl-1.3,2-dioxaborinane (2.0 eq.), in dry toluene/ethanol,(3/1 mL) was degassed by argon bubbling for 15 min. Pd(PPh3)4 (0.05 eq.) was addedand the mixture was heated to 150 °C for 1 h by microwave irradiation. The solvent wasremoved in vacuo. The crude product was purified by flash chromatography.
  • 61
  • [ 1118762-80-3 ]
  • [ 4627-10-5 ]
  • methyl (2E,4E,6E)-7-(4,4,6-trimethyl-1,3,2-dioxaborinane-2-yl)hepta-2,4,6-trienoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
48% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 19.5h; Inert atmosphere;
21% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 48h; Schlenk technique; Inert atmosphere; 4.2.3. Methyl (2E,4E,6E)-7-(4,4,6-trimethyl-1,3,2-dioxaborinane-2-yl)hepta-2,4,6-trienoate 25 Method 1: To a dry Schlenk flask was added Pd(OAc)2 (16 mg, 0.071 mmol), P(o-tol)3 (43 mg, 0.14 mmol) and AgOAc (0.284 g,1.7 mmol), followed by a solution of (2E,4E)-5-iodopenta-2,4-dienoate (0.337 g, 1.42 mmol) in dry, degassed MeCN (4.5 mL). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.24 mL, 1.4 mmol) was then added and the reaction mixture was then heated to 50 °C with vigorous stirring for 2 days. The mixture was allowed to cool, then diluted with Et2O (80 mL) and passed through a short Celite/silica plug. The organic extracts were washed with H2O (40 mL) and brine (40 mL), dried over MgSO4, filtered and evaporated to yield crude product (0.33 g) as an orange oil. The crude product was purified by silica gel chromatography, eluent 10% EtOAc in hexane, to yield methyl (2E,4E,6E)-7-(4,4,6-trimethyl-1,3,2-dioxaborinane-2-yl)hepta-2,4,6-trienoate as a pale yellow solid (78 mg, 21%), mp 80.1-82.1 °C. 1H NMR (400 MHz, CDCl3): δ 1.36-1.23 (9H, m),1.56-1.47 (1H, m), 1.80 (1H, dd, J=13.9, 3.0 Hz), 3.75 (3H, s), 4.24 (1H, ddp, J=12.3, 6.2, 3.2 Hz), 5.71 (1H, d, J =17.4 Hz), 5.92 (1H, d, J=15.3 Hz), 6.46-6.33 (1H, m), 6.58 (1H, ddd, J=15.0, 10.7, 0.9 Hz), 6.97 (1H, dd, J=17.4, 10.7 Hz), 7.35-7.27 (1H, m); 11B NMR (128 MHz, CDCl3): δ 25.90; 13C NMR (101 MHz, CDCl3): δ 23.1, 28.1,31.2, 46.0, 51.6, 64.9, 71.0, 121.5, 131.7, 142.4, 144.5, 145.2, 167.4; IR (νmax, cm-1) 2972.0 (w), 2949.7 (w), 2924.1 (w) 1705.9 (s) inter alia; LCMS (ESI) 264.1; HRMS (ESI) calculated [C14H21BO4H] 264.1620, found 264.1647. Method 2: To a dry flask was added Pd(OAc)2 (0.120 g, 0.525 mmol), P(o-tol)3 (0.315 g, 1.50 mmol) and AgOAc (1.89 g,11.3 mmol). The flask was purged with argon, and a solution of (2E,4E)-5-iodopenta-2,4-dienoate (2.50 g, 10.5 mmol) in dry,degassed MeCN (63 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (2.2 mL, 13 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was then heated to 50 °C with vigorous stirring for 19.5 h. The mixture was allowed to cool, then diluted with Et2O (180 mL) and passed through a short Celite/silica plug. The organic extracts were washed with NH4Cl (180 mL), H2O (180 mL) and brine (100 mL), dried over MgSO4, filtered, evaporated and dried on the high vacuum line for 2 days to give crude product as a brown oil (1.7 g, 48% from starting acrylate). The compound was taken on to the next stage without any further purification or characterisation. Method 3: To a dry flask was added Pd(OAc)2 (0.102 g, 0.460 mmol), P(o-tol)3 (0.276 g, 0.911 mmol) and AgOAc (1.64 g,9.81 mmol), followed by a solution of (2E,4E)-5-iodopenta-2,4-dienoate (2.14 g, 8.99 mmol) in dry, degassed MeCN (54 mL). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (1.8 mL, 10 mmol) was then added and the reaction mixture was then heated to 30 °C with vigorous stirring for 18.5 h. The mixture was allowed to cool, then diluted with Et2O (136 mL) and passed through a short Celite/silica plug. The solvent was evaporated to yield 3.8 g of a crude yellow solid containing desired product (8.67 mmol, 96% as determined by1H NMR spectroscopy). This material was taken on to the next stage without any further purification or characterisation. Method 4: To a dry flask was added methyl (2E,4E)-5-iodopenta-2,4-dienoate (1.09 g, 4.58 mmol), Pd(OAc)2 (9.5 mg, 0.043 mmol), tri(2-furyl)phosphine (0.020 g, 0.085 mmol) and AgOAc (0.766 g,4.6 mmol). The flask was purged with argon, and dry, degassed MeCN (25 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.84 mL, 4.9 mmol) was then added, the vessel was purged further with argon, and the reaction mixture was stirred vigorously at room temperature for 20 h. The mixture was diluted with Et2O (64 mL) and passed through a short Celite/silicaplug. The solvent was evaporated to give crude product as a dark orange oil (1.18 g, 100%). The compound was taken on to the next stage without any further purification or characterisation.
  • 62
  • methyl (2E,4E,6E)-7-iodohepta-2,4,6-trienoate [ No CAS ]
  • [ 4627-10-5 ]
  • methyl (2E,4E,6E,8E)-9-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)nona-2,4,6,8-tetraenoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 30℃; for 15.5h;
21% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 30℃; for 18h; 4.2.5. Methyl (2E,4E,6E,8E)-9-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)nona-2,4,6,8-tetraenoate 27 Method 1: To a dry flask was added Pd(OAc)2 (82 mg,0.36 mmol), P(o-tol)3 (0.214 g, 0.714 mmol) and AgOAc (1.29 g, 7.71 mmol), followed by a solution of methyl (2E,4E,6E)-7-iodohepta-2,4,6-trienoate (1.70 g, 6.44 mmol) in dry, degassed MeCN (43 mL), which had been previously degassed by a bubbling argon needle. 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane (1.5 mL,8.6 mmol) was then added and the reaction mixture was then heated to 50 °C with vigorous stirring for 21 h. The mixture was allowed to cool, then diluted with Et2O (150 mL) and passed through a short Celite/silica plug. The organic extracts were washed with H2O (150 mL) and brine (150 mL), dried over MgSO4, filtered and evaporated to yield 2.2 g of crude product as a brown oil. After drying the crude product on the high vacuum line for 2 days,1.2 g of an orange solid was obtained. The compound was taken on to the next stage without any further purification or characterisation. Method 2: To a dry flask was added PdOAc)2 (98 mg,0.44 mmol), P(o-tol)3 (0.265 g, 0.875 mmol) and AgOAc (1.57 g, 9.42 mmol), followed by a solution of methyl (2E,4E,6E)-7-iodohepta-2,4,6-trienoate (2.28 g, 8.60 mmol) in dry, degassed MeCN (52 mL). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (1.4 mL, 8.6 mmol) was then added and the reaction mixture was then heated to 30 °C with vigorous stirring for 15.5 h. The mixture was allowed to cool, then diluted with Et2O (131 mL) and passed through a short Celite/silica plug. The solvent was evaporated to yield 3.95 g of a crude viscous orange oil containing desired product (1.90 g, 76%). After drying the crude product on the high vacuum line for 2 days,1.2 g of an orange solid was obtained. The compound was taken on to the next stage without any further purification or characterisation. Method 3: To a dry flask was added Pd(OAc)2 (0.134 g, 0.440 mmol), P(o-tol)3 (0.364 g, 1.20 mmol) and AgOAc (2.16 g,13.0 mmol), followed by a solution of methyl (2E,4E,6E)-7-iodohepta-2,4,6-trienoate (3.14 g, 11.9 mmol) in dry, degassed MeCN (72 mL). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (2.0 mL, 12 mmol) was then added and the reaction mixture was then heated to 30 °C with vigorous stirring for 18 h. The mixture was allowed to cool, then diluted with Et2O (180 mL) and passed through a short Celite/silica plug. The solvent was evaporated to yield 4.5 g of a crude viscous orange oil. The crude product was purified by silica gel chromatography, eluent 5% EtOAc in petroleum ether, to give desired product as a bright yellow solid (0.90 g, 23% from iodoacrylate). 1H NMR (700 MHz, CDCl3): δ 1.23-1.33 (9H, m),1.45-1.56 (1H, m), 1.79 (1H, dd, J=13.9, 2.9 Hz), 3.74 (3H, s), 4.22(1H, ddt, J=11.5, 6.1, 2.9 Hz), 5.59e5.65 (1H, m), 5.84-5.93 (1H, m), 6.27-6.46 (3H, m), 6.54-6.63 (1H, m), 6.91-7.00 (1H, m), 7.28-7.37(1H, m); 11B NMR (128 MHz, CDCl3): δ 25.92; 13C NMR (176 MHz,CDCl3): d 23.1, 28.1, 31.2, 45.9, 51.5, 64.8, 70.9, 110.1, 120.6, 130.9,133.6, 138.9, 140.6, 144.4, 145.8, 167.4; LCMS (ASAP) [M+H] 291.2; HRMS (ASAP) calculated [C16H2410BO4] 290.1804, found 290.1777. The compound was taken on to the next stage without any further purification or characterisation. Method 4: To a dry flask was added methyl (2E,4E,6E)-7-iodohepta-2,4,6-trienoate (0.737 g, 2.83 mmol), Pd(OAc)2 (6.4 mg, 0.028 mmol), tri(2-furyl)phosphine (0.013 g, 0.056 mmol) and AgOAc (0.511 g, 3.07 mmol). The flask was purged with argon, and dry, degassed MeCN (17 mL) was added. 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.56 mL, 3.2 mmol) was then added, the vessel was purged further with argon, and the reaction mixture wasstirred vigorously at room temperature for 25 h. The mixture was diluted with Et2O (43 mL) and passed through a short Celite/silicaplug. The solvent was evaporated to give crude product as a dark orange oil (1.21 g) containing desired product (2.15 mmol, 76% as determined by 1H NMR spectroscopy. The compound was taken onto the next stage without any further purification or characterisation.
  • 63
  • [ 637-69-4 ]
  • [ 4627-10-5 ]
  • 2-[(E)-2-(4-Methoxy-phenyl)-vinyl]-4,4,6-trimethyl-[1,3,2]dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With Ru(CO)(Cl)H(PCy<SUB>3</SUB>)<SUB>2</SUB> at 110℃; for 18h; Schlenk technique; Inert atmosphere; Green chemistry; stereoselective reaction; 2.2.2. Borylative coupling under repetitive batch mode - Aliphaticsolvent extraction General procedure: A 50 mL Schlenk vessel was charged with dried PEG (1 g) and[Ru(CO)Cl(H)(PCy3)2] (0.01 mmol) under an argon atmosphere. Subsequently, vinyl boronate (0.5 mmol) and olefin (1.0 mmol)were added. The reaction was carried out for 18 h at 110 °C. Thereaction mixture was cooled to room temperature and the products were extracted with aliphatic solvent: n-hexane or n-heptane(3 5 mL) and analyzed by GC-MS analysis. The residual amount of solvent was evaporated under a vacuum and a new portion of substrates was added under an argon atmosphere, and subsequent batches and extractions were carried out under the above-described conditions.
  • 64
  • [ 4627-10-5 ]
  • (E)-1,2-bis(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)ethene [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With carbon dioxide; Ru(CO)(Cl)H(PCy<SUB>3</SUB>)<SUB>2</SUB> at 110℃; for 18h; Schlenk technique; Inert atmosphere; Green chemistry; stereoselective reaction; 2.2.2. Borylative coupling under repetitive batch mode - Aliphaticsolvent extraction General procedure: A 50 mL Schlenk vessel was charged with dried PEG (1 g) and[Ru(CO)Cl(H)(PCy3)2] (0.01 mmol) under an argon atmosphere. Subsequently, vinyl boronate (0.5 mmol) and olefin (1.0 mmol)were added. The reaction was carried out for 18 h at 110 °C. Thereaction mixture was cooled to room temperature and the products were extracted with aliphatic solvent: n-hexane or n-heptane(3 5 mL) and analyzed by GC-MS analysis. The residual amount of solvent was evaporated under a vacuum and a new portion of substrates was added under an argon atmosphere, and subsequent batches and extractions were carried out under the above-described conditions.
  • 65
  • [ 622-97-9 ]
  • [ 4627-10-5 ]
  • 4,4,6-trimethyl-2-(2-<i>p</i>-tolyl-vinyl)-[1,3,2]dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With Ru(CO)(Cl)H(PCy<SUB>3</SUB>)<SUB>2</SUB> at 110℃; for 18h; Schlenk technique; Inert atmosphere; Green chemistry; stereoselective reaction; 2.2.2. Borylative coupling under repetitive batch mode - Aliphaticsolvent extraction General procedure: A 50 mL Schlenk vessel was charged with dried PEG (1 g) and[Ru(CO)Cl(H)(PCy3)2] (0.01 mmol) under an argon atmosphere. Subsequently, vinyl boronate (0.5 mmol) and olefin (1.0 mmol)were added. The reaction was carried out for 18 h at 110 °C. Thereaction mixture was cooled to room temperature and the products were extracted with aliphatic solvent: n-hexane or n-heptane(3 5 mL) and analyzed by GC-MS analysis. The residual amount of solvent was evaporated under a vacuum and a new portion of substrates was added under an argon atmosphere, and subsequent batches and extractions were carried out under the above-described conditions.
  • 66
  • methyl (2E,4E,6E,8E)-9-iodonona-2,4,6,8-tetraenoate [ No CAS ]
  • [ 4627-10-5 ]
  • methyl (2E,4E,6E,8E,10E)-11-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)undeca-2,4,6,8,10-pentaenoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 21h; 4.2.7. Methyl (2E,4E,6E,8E,10E)-11-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)undeca-2,4,6,8,10-pentaenoate To a dry flask was added Pd(OAc)2 (45 mg, 0.20 mmol), P(o-tol)3(0.117 g, 0.394 mmol) and AgOAc (0.713 g, 4.26 mmol), followed by a solution of methyl (2E,4E,6E,8E)-9-iodonona-2,4,6,8-tetraenoate (1.10 g, 3.79 mmol) in dry, degassed MeCN (24 mL). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.75 mL, 4.3 mmol) was then added and the reaction mixture was then heated to 50 °C with vigorous stirring for 21 h. The mixture was allowed to cool, then diluted with Et2O (100 mL) and passed through a short Celite/silicaplug. The organic extracts were washed with H2O (100 mL) and brine (100 mL), dried over MgSO4, filtered and evaporated to yield 1.2 g of crude product a deep red solid. A small portion (0.153 g) was taken and purified by silica gel chromatography, eluent 10% EtOAc in petroleum ether to verify presence of product. 1H NMR (400 MHz, CDCl3): δ 1.21-1.35 (9H, m), 1.41-1.51 (1H, m), 1.72-1.88 (1H, m), 3.74 (3H, s), 4.23 (1H, ddh, J=12.2, 6.2, 2.9 Hz), 5.56-5.68 (1H, m), 5.88 (1H, d, J=15.3 Hz), 6.25-6.50 (5H, m), 6.92-7.02 (1H,m), 7.32 (1H, ddd, J=13.0, 11.0, 3.7 Hz); 11B NMR (128 MHz, CDCl3) δ 23.80.
  • 67
  • 2-[(E)-2-(4-bromo-3-methoxyphenyl)ethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ No CAS ]
  • [ 4627-10-5 ]
  • 2-[(1E,3E)-4-(4-bromo-3-methoxyphenyl)buta-1,3-dien-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 18h; Inert atmosphere; 4.2.9. 2-[(1E,3E)-4-(4-Bromo-3-methoxyphenyl)buta-1,3-dien-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane 17 Method 1: 1-Bromo-4-[(E)-2-iodoethenyl]-2-methoxybenzene (0.863 g, 2.55 mmol) was dissolved in dry, degassed MeCN (15 mL) and added to a dry, argon-purged flask containing Pd(OAc)2 (29 mg, 0.13 mmol), P(o-tol)3 (77 mg, 0.26 mmol) and AgOAc (0.458 g, 2.74 mmol). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.50 mL, 2.9 mmol) was then added and the reaction mixture heated to 50 °C for 18 h. The reaction mixture was allowed to cool to room temperature, then diluted with Et2O containing ~3 ppm BHT (38 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give 1.37 g of crude product as a viscous orange oil. The crude product was purified by silica gel chromatography, elution gradient 0-10% EtOAc in petroleum ether. Pure fractions were evaporated to give desired product as a viscous yellow oil(0.725 g, 78%). 1H NMR (600 MHz, CDCl3): δ 1.23-1.33 (9H, m),1.46-1.53 (1H, m), 1.80 (1H, ddd, J=14.0, 11.2, 2.9 Hz), 3.92 (3H, s), 4.24 (1H, dddq, J=14.8, 9.0, 6.1, 3.1 Hz), 5.64 (1H, d, J=17.4 Hz), 6.59 (1H, d, J=15.6 Hz), 6.77-6.84 (1H, m), 6.87-6.94 (2H, m), 7.06 (1H, dd, J=17.3, 10.5 Hz), 7.42-7.47 (1H, m); 11B NMR (128 MHz, CDCl3): δ 25.56; 13C NMR (151 MHz, CDCl3): δ 23.1, 28.1, 31.2, 46.0,64.8, 70.8, 109.7, 111.3, 120.3, 131.7, 133.3, 133.6, 134.9, 137.9, 146.3,155.9; LRMS (ASAP) [MH] 365.1; HRMS (ASAP) [C17H2310BO3Br] calculated 364.0960, found 364.0958. Method 2: 1-Bromo-4-[(E)-2-iodoethenyl]-2-methoxybenzene (1.40 g, 4.15 mmol) was dissolved in dry, degassed MeCN (24 mL)and added to a dry, argon-purged flask containing Pd(OAc)2 (46 mg,0.21 mmol), P(o-tol)3 (0.123 g, 0.41 mmol) and AgOAc (0.733 g,4.38 mmol). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.80 mL,4.8 mmol) was then added and the reaction mixture heated to 30 °C for 21.5 h. The reaction mixture was allowed to cool to room temperature, then diluted with Et2O containing ~3 ppm BHT (61 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give 1.67 g of crude product as a viscous orange oil. The crude product was purified by silica gel chromatography, elution gradient 0-10% EtOAc in petroleum ether. Pure fractions were evaporated to give desired product as a viscous yellow oil (1.10 g, 73% over the two steps).
  • 68
  • 1-bromo-4-[(1E,3E)-4-iodobuta-1,3-dien-1-yl]-2-methoxybenzene [ No CAS ]
  • [ 4627-10-5 ]
  • 2-[(1E,3E,5E)-6-(4-bromo-3-methoxyphenyl)hexa-1,3,5-trien-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 50℃; for 65h; Inert atmosphere; 4.2.11. 2-[(1E,3E,5E)-6-(4-Bromo-3-methoxyphenyl)hexa-1,3,5-trien-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane 19 Method 1: 1-Bromo-4-[(1E,3E)-4-iodobuta-1,3-dien-1-yl]-2-methoxybenzene (0.708 g, 1.95 mmol) was dissolved in dry, degassed MeCN (11.6 mL) and added to a dry, argon-purged flask containing Pd(OAc)2 (22 mg, 0.10 mmol), P(o-tol)3 (59 mg,0.190 mmol) and AgOAc acetate (0.348 g, 2.08 mmol). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.38 mL, 2.2 mmol) was then added and the reaction mixture heated to 50 °C for 2 days 17 h. The reaction mixture was allowed to cool to room temperature then diluted with Et2O containing ~3 ppm BHT (29 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give 1.031 g of crude product as a brown oil. The crude product was purified by silica gel chromatography, elution gradient 0-10% EtOAc in petroleum ether. Pure fractions were evaporated to yield desired product as a bright yellow oil (0.470 g, 62%). 1H NMR (600 MHz, CDCl3): δ 1.14-1.9 (1H, m), 1.46-1.55 (1H, m), 1.80 (1H,dd, J=13.9, 2.9 Hz), 3.92 (3H, s), 4.24 (1H, dqd, J=12.3, 6.2, 3.0 Hz), 5.58 (1H, d, J=17.4 Hz), 6.39-6.55 (3H, m), 6.82 (1H, dd, J=15.5,10.0 Hz), 6.82-6.92 (2H, m), 7.00 (1H, dd, J=17.3, 9.9 Hz), 7.45 (1H,d, J=8.1 Hz); 11B NMR (128 MHz, CDCl3): δ 25.49; 13C NMR (151 MHz, CDCl3): δ 23.3, 28.3, 31.4, 46.2, 56.3 (OMe), 65.0, 71.0, 109.5, 111.0, 120.3, 130.0, 132.7, 133.5, 134.8, 136.2, 138.2, 146.5,156.1; LRMS (ASAP) [MH] 391.1; HRMS (ASAP) [C19H2410BO3Br] calculated 389.1038, found 389.1023. Method 2: 1-Bromo-4-[(1E,3E)-4-iodobuta-1,3-dien-1-yl]-2-methoxybenzene (1.0 g, 2.8 mmol) was dissolved in dry, degassed MeCN (16 mL) and added to a dry, argon-purged flask containing Pd(OAc)2 (31 mg, 0.14 mmol), P(o-tol)3 (83 mg, 0.27 mmol) and AgOAc (0.491 g, 2.93 mmol). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.53 mL, 3.1 mmol) was then added and the reaction mixture heated to 30 °C for 18 h. The reaction mixture was allowed to cool to room temperature then diluted with Et2O containing ~ 3 ppm BHT (41 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give 1.10 g of crude product as aviscous orange oil. The crude product was purified by silica gel chromatography, elution gradient 0-10% EtOAc in petroleum ether. Pure fractions were evaporated to yield desired product as a viscous yellow oil (0.600 g, 56%).
  • 69
  • 1-bromo-4-[(1E,3E,5E)-6-iodohexa-1,3,5-trien-1-yl]-2-methoxybenzene [ No CAS ]
  • [ 4627-10-5 ]
  • 2-[(1E,3E,5E,7E)-8-(4-bromo-3-methoxyphenyl)octa-1,3,5,7-tetraen-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine In acetonitrile at 30℃; for 18.5h; Inert atmosphere; 4.2.13. 2-[(1E,3E,5E,7E)-8-(4-Bromo-3-methoxyphenyl)octa-1,3,5,7-tetraen-1-yl]-4,4,6-trimethyl-1,3,2-dioxaborinane 21 Method 1: 1-Bromo-4-[(1E,3E,5E)-6-iodohexa-1,3,5-trien-1-yl]-2-methoxybenzene (0.233 g, 0.60 mmol) was dissolved in dry, degassed MeCN (3.7 mL) and added to a dry, argon-purged flask containing Pd(OAc)2 (7.0 mg, 0.031 mmol), P(o-tol)3 (18 mg, 0.060 mmol) and AgOAc (0.109 g, 0.645 mmol). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.12 mL, 0.69 mmol) was then added and the reaction mixture heated to 50 °C for 20 h. The reaction mixture was allowed to cool to room temperature, then dilutedwith Et2O containing ~3 ppm BHT (25 mL) and passed through ashort Celite/silica plug. The solvent was evaporated to give 0.296 g of crude product as a dark red viscous oil. The crude product was purified by silica gel chromatography, elution gradient 0-10% EtOAc in petroleum ether. Pure fractions were evaporated to give desired product as a bright orange gum (0.146 g, 58%). Method 2: 1-Bromo-4-[(1E,3E,5E)-6-iodohexa-1,3,5-trien-1-yl]-2-methoxybenzene (0.506 g, 1.30 mmol) was dissolved in dry, degassed MeCN (7.8 mL) and added to a dry, argon-purged flask containing Pd(OAc)2 (15 mg, 0.067 mmol), P(o-tol)3 (39 mg, 0.13 mmol) and AgOAc (0.232 g, 1.39 mmol). 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane (0.25 mL, 1.5 mmol) was then added and the reaction mixture heated to 30 °C for 18.5 h. The reaction mixture was allowed to cool to room temperature, then diluted with Et2O containing ~3 ppm BHT (19 mL) and passed through a short Celite/silica plug. The solvent was evaporated to give 0.704 g of crude product as a dark red viscous oil. The crude product was purified by silica gel chromatography, elution gradient 0-10% EtOAc in petroleum ether. Pure fractions were evaporated to give desired product as a bright orange gum (0.289 g, 53%). 1H NMR (600 MHz, CDCl3): δ 1.24-1.6 (9H, m), 1.46-1.54 (1H, m), 1.79 (1H,dd, J=13.8, 3.0 Hz), 3.92 (3H, s), 4.24 (1H, ddqd, J=12.3, 9.1, 6.0,2.9 Hz), 5.55 (1H, d, J=17.3 Hz), 6.03-6.18 (1H, m), 6.39-6.44 (3H,m), 6.48-6.52 (1H, m), 6.84-6.94 (3H, m), 6.95-7.04 (1H, m), 7.45(1H, d, J=8.1 Hz); 11B NMR (128 MHz, CDCl3): δ 25.37; 13C NMR (151 MHz, CDCl3): δ 23.3, 28.3, 31.4, 46.2, 56.3, 64.9, 71.0, 109.6,110.9, 120.2, 129.7, 130.0, 132.0, 133.5, 134.1, 134.2, 135.1, 135.8,138.3, 146.7, 156.1; IR (υmax, cm-1) 1568.7 (m), 1587.0 (m), 1607.7(m), 2911.1 (m), 2938.7 (m), 2971.6 (m) inter alia; LRMS (ASAP) [MH] 417.1; HRMS (ESI) [C21H2610BO3Br] calculated 415.1195, found 415.1213.
  • 70
  • [ 6213-88-3 ]
  • [ 4627-10-5 ]
  • [ 935464-66-7 ]
  • [ 2409-87-2 ]
YieldReaction ConditionsOperation in experiment
With silver(I) acetate; palladium diacetate; tris-(o-tolyl)phosphine; In acetonitrile; at 20℃; for 3h;Inert atmosphere; Darkness; Methyl (2E)-3-iodoprop-2-enoate (0.141 g, 0.665 mmol), Pd(OAc)2 (15 mg, 0.067 mmol), ligand (0.13 mmol) and AgOAc (0.120 g, 0.721 mmol) were added to dry flasks under argon in the absence of light. Degassed MeCN (4.0 mL) was added to each flask, followed by 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane (0.13 mL, 0.76 mmol) under a positive pressure of argon. The flasks were then purged with argon for 2 min, and then stirred vigorously at room temperature, with conversion monitored at 1.5 h, 3 h and 24 h by 1HNMR. The HM:SM ratio was also determined by 1H NMR spectroscopy.
  • 71
  • [ 15761-39-4 ]
  • [ 13329-40-3 ]
  • [ 4627-10-5 ]
  • [ 1622835-73-7 ]
  • 2-(4-acetylphenyl) 1-(tert-butyl) pyrrolidine-1,2-dicarboxylate [ No CAS ]
  • tert-butyl 2-(4-acetylphenethyl)pyrrolidine-1-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 17% 2: 20% 3: 18% Stage #1: 1-(tert-butoxycarbonyl)-L-proline; 4-Iodoacetophenone; 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; Sealed tube; Irradiation; Stage #2: With urea hydrogen peroxide adduct In N,N-dimethyl acetamide at 0 - 20℃; for 1h;
  • 72
  • [ 15761-39-4 ]
  • [ 352-34-1 ]
  • [ 4627-10-5 ]
  • tert-butyl 2-(2-(4-fluorophenyl)-2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)ethyl)pyrrolidine-1-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
27 mg With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 16h; Sealed tube; Irradiation;
  • 73
  • [ 352-34-1 ]
  • [ 1148-11-4 ]
  • [ 4627-10-5 ]
  • C26H33BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
4 % de With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 74
  • [ 352-34-1 ]
  • [ 159749-28-7 ]
  • [ 4627-10-5 ]
  • C22H33BFNO4 [ No CAS ]
  • 75
  • [ 352-34-1 ]
  • [ 26250-84-0 ]
  • [ 4627-10-5 ]
  • C24H37BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 76
  • [ 352-34-1 ]
  • (5R)-3-(tert-butoxycarbonyl)-2,2,5-trimethyloxazolidine-4-carboxylic acid [ No CAS ]
  • [ 4627-10-5 ]
  • C25H39BFNO5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
2 % de With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 77
  • [ 352-34-1 ]
  • [ 203869-80-1 ]
  • [ 4627-10-5 ]
  • C24H37BFNO4 [ No CAS ]
  • 78
  • [ 352-34-1 ]
  • [ 13734-36-6 ]
  • [ 4627-10-5 ]
  • C21H33BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 79
  • [ 15761-38-3 ]
  • [ 352-34-1 ]
  • [ 4627-10-5 ]
  • C21H33BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
8 % de With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 80
  • [ 352-34-1 ]
  • [ 16948-16-6 ]
  • [ 4627-10-5 ]
  • C22H35BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
16 % de With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 81
  • [ 352-34-1 ]
  • [ 30992-29-1 ]
  • [ 4627-10-5 ]
  • C22H35BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 48h; Sealed tube; Irradiation;
  • 82
  • [ 352-34-1 ]
  • [ 146000-39-7 ]
  • [ 4627-10-5 ]
  • C23H37BFNO4 [ No CAS ]
  • 83
  • [ 352-34-1 ]
  • [ 14463-79-7 ]
  • [ 4627-10-5 ]
  • C25H29BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
  • 84
  • [ 13734-41-3 ]
  • [ 352-34-1 ]
  • [ 4627-10-5 ]
  • C23H37BFNO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
6 % de With (1,2-dimethoxyethane)dichloronickel(II); (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; caesium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 25 - 30℃; for 24h; Sealed tube; Irradiation;
Same Skeleton Products
Historical Records