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[ CAS No. 214360-65-3 ] {[proInfo.proName]}

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Chemical Structure| 214360-65-3
Chemical Structure| 214360-65-3
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Quality Control of [ 214360-65-3 ]

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Product Details of [ 214360-65-3 ]

CAS No. :214360-65-3 MDL No. :MFCD05863924
Formula : C13H16BF3O2 Boiling Point : -
Linear Structure Formula :C(CH3)2C(CH3)2O2B(C6H4CF3) InChI Key :GCQADNWXVSTJQW-UHFFFAOYSA-N
M.W : 272.07 Pubchem ID :2760605
Synonyms :

Calculated chemistry of [ 214360-65-3 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 19
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.54
Num. rotatable bonds : 2
Num. H-bond acceptors : 5.0
Num. H-bond donors : 0.0
Molar Refractivity : 67.92
TPSA : 18.46 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : Yes
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.27 cm/s

Lipophilicity

Log Po/w (iLOGP) : 0.0
Log Po/w (XLOGP3) : 3.79
Log Po/w (WLOGP) : 4.16
Log Po/w (MLOGP) : 2.68
Log Po/w (SILICOS-IT) : 2.87
Consensus Log Po/w : 2.7

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -4.02
Solubility : 0.0262 mg/ml ; 0.0000963 mol/l
Class : Moderately soluble
Log S (Ali) : -3.87
Solubility : 0.0366 mg/ml ; 0.000134 mol/l
Class : Soluble
Log S (SILICOS-IT) : -4.88
Solubility : 0.00356 mg/ml ; 0.0000131 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.81

Safety of [ 214360-65-3 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P270-P273-P301+P312-P330 UN#:N/A
Hazard Statements:H302-H413 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 214360-65-3 ]

* 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 [ 214360-65-3 ]

[ 214360-65-3 ] Synthesis Path-Downstream   1~101

  • 1
  • [ 98-08-8 ]
  • [ 25015-63-8 ]
  • [ 325142-82-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
General procedure: [RuCl2(p-cymene)]2 (2.3 mg, 3.8 mumol) and TpMe2K (2.5 mg, 7.5 mumol)were placed in a resealable Schlenk tube. The tube was evacuated,backfilled with dinitrogen and then charged with the arene 2 (5 mmol).After stirring the mixture at room temperature for 1 h, pinacolborane(1; 36 muL, 0.25 mmol) was added. The reaction mixture was thenstirred at 120 C for 16 h. After the reaction, the mixture was analysedby GC and GC-MS. The volatile material was removed in vacuo, andthe residue was purified by Kugelrohr distillation.
  • 2
  • [ 98-08-8 ]
  • [ 73183-34-3 ]
  • [ 325142-82-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
With bis(1,5-cyclooctadiene)nickel (0); 1,3-bis(mesityl)imidazolium chloride; sodium t-butanolate; at 140℃; for 24h;Inert atmosphere; Glovebox; Sealed tube; General procedure: A 20-mL glass vessel equipped with J. Young O-ring tap containing a magnetic stirring bar was dried with a heat-gun under reduced pressure and filled with nitrogen after cooling to room temperature. After adding bis(pinacolato)diboron (127.0 mg, 0.5 mmol), the vessel was introduced inside an argon-atmosphere glovebox. In the glovebox, Ni(cod)2 (13.8 mg, 0.05 mmol) and CsF (19.0 mg, 0.125 mmol) were added to the vessel, which was sealed with O-ring tap and then taken out of the glovebox. Then, PCyp3 (23.8 mg, 0.1 mmol) and benzene derivative 1 (3.0 mL) were added to the vessel under nitrogen atmosphere. The vessel was heated at 140 C for 24 h in an oil bath with stirring. After cooling the reaction mixture to room temperature, the mixture was concentrated and directly purified by preparative thin-layer chromatography (PTLC; hexane/ethyl acetate as the eluent) to afford the borylation product 2. Yields of 2 are calculated based on bis(pinacolato)diboron.
  • 3
  • [ 98-56-6 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
94% With potassium acetate; palladium diacetate; (1R,3S,5S,7R)-8-([1,1'-biphenyl]-2-yl)-1,3,5,7-tetramethyl-2,4,6-trioxa-8-phospha-adamantane In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; Sealed tube; General procedure for room temperature borylation (A). General procedure: An oven-dried ace pressure tube was evacuated and backfilled with argon. Pd(OAc)2 (0.005 - 0.02 mmol, 0.5 - 2 mol%) and ligand (0.0125 - 0.05 mmol, 1.25 - 5 mol%), were added and the tube was evacuated and backfilled with argon. THF (2.00 mL), aryl halide (1mmol), bis(pinacolato)diboron (2 - 3 mmol), KOAc (3 mmol), and n-decane (0.5 mmol, internal standard), were added to the tube. The tube underwent a final evacuation/backfill cycle, sealed with a screw cap, and allowed to stir at room temperature (25 °C) for the specified times (1 - 12 h). Conversion, selectivity and GC yield were quantified from an aliquot (0.20 mL) of the reaction mixture using GC-FID. Upon completion, the GC sample was transferred back into the main reaction mixture, an aqueous work-up was performed (EtOAc:H2O, 1:1). The organic layer was dried over MgSO4, filtered through a cotton wool plug and concentrated on a rotary evaporator. The isolated yield was obtained by purification of the crude product through column chromatography using silica gel (EtOAc-hexane).
90% With tris-(dibenzylideneacetone)dipalladium(0); 2-(2-methoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; potassium acetate In 1,4-dioxane at 110℃; for 24h; Inert atmosphere;
90% With cerium(III) chloride; tetraethylammonium chloride In acetonitrile at 20℃; for 24h; Irradiation; Inert atmosphere; Sealed tube;
90% With bis(1,3-dimesityl-1H-imidazol-2(3H)-ylidene)nickel(0); potassium methanolate In hexane at 25℃; for 6h; Inert atmosphere; Irradiation;
90% Stage #1: 4-chlorobenzotrifluoride; bis(pinacol)diborane With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; XPhos at 110℃; for 6h; Schlenk technique; Inert atmosphere; Stage #2: Inert atmosphere; Palladium-Catalyzed Borylation of Aryl Chlorides in PEG-2000;General Procedure General procedure: To a dried Schlenk tube were added Pd2dba3 (4.6 mg, 0.005 mmol),XPhos (9.6 mg, 0.02 mmol), bis(pinacolato)diboron (190 mg, 0.75mmol), PEG-2000 (1.0 g), and KOAc (147 mg, 1.5 mmol). The Schlenktube was evacuated and backfilled with argon. The reaction mixturewas heated to 50 °C, followed by the addition of the aryl chloride (0.5mmol) via syringe (aryl chlorides that were solid were added withother reagents before evacuation). The reaction mixture was thenstirred at 110 °C under Ar for 6 h. After being cooled to 45 °C, the resultingmixture was extracted with cyclohexane (3 × 5 mL). The residueof the extraction was subjected to a second run of the borylationreaction by charging with the same substrates (aryl chloride, bis(pinacolato)diboron and KOAc) under the same conditions without furtheraddition of Pd2dba3 and XPhos. The combined cyclohexane layerwas concentrated under reduced pressure. The residue was purifiedby flash column chromatography on silica gel using a mixture of petroleumether and EtOAc as eluent or by recrystallization from hexaneto afford the desired aryl boronates 2.
89% With dichloro(cycloocta-1,5-diene)palladium (II); potassium acetate In benzene at 60℃; for 10h; Inert atmosphere;
89% With catalyst: silica-SMAP/PdCl2(1,5-cyclooctadiene); K(CH3COO) In benzene soln. of Pd complex in benzene and aryl halide added to mixt. of silica-SMAP, B compd., and KOAc in degassed benzene in glass tube with stirrer,tube sealed with screw cap, removed from glove box, mixt. stirred at 60 °C for 10 h; soln. filtered through Celite pad, filtrate evapd. under vac., column chromy. (silica gel, EtOAc/hexane 1/9);
86% With pyridine-4-carbonitrile; potassium phosphate; sodium oxalate; 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile In acetonitrile at 20℃; for 24h; Irradiation; Inert atmosphere; Sealed tube;
80% With [1,3-bis(cyclohexyl)imidazol-2-ylidene]copper(I) chloride; potassium <i>tert</i>-butylate In methyl cyclohexane at 90℃; for 42h; Inert atmosphere; Glovebox;
79% With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; potassium acetate In benzene at 25℃; for 10h; Inert atmosphere; Sealed tube; Typical Procedure for Miyaura Borylation of Chloroarenes (Figure 1 and Table 1) General procedure: In a nitrogen-filled glove box, Silica-3p-TPP ([P] 0.11 mmol/g, 45.5 mg, 0.005 mmol P, 1 mol % P), anhydrous, degassed benzene (0.8 mL), and a solution of [PdCl(η3-cinnamyl)]2 (0.65 mg, 0.00125 mmol, 0.5 mol % Pd) in benzene (0.2 mL) were placed in an oven-dried, 10-mL glass tube containing a magnetic stirring bar. After stirring of the mixture for 5 min, KOAc (147 mg, 1.5 mmol), bis(pinacolato)diboron (2, 140 mg, 0.55 mmol), and p-chlorotoluene (1a, 63.3 mg, 0.50 mmol) were added. The tube was sealed with a screw cap and was removed from the glove box. The mixture was stirred at 25 °C for 10 h, and was filtered through a Celite pad (eluting with Et2O). Solvent was removed under reduced pressure. An internal standard (1,1,2,2-tetrachloroethane) was added to a residue to determine the yield of the product by 1H NMR (95%). The crude material was then purified by silica gel chromatography to give arylboronate 3a (87.0 mg, 0.40 mmol, 80% yield).
77% With potassium acetate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride In tetrahydrofuran for 5h; Heating;
77% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0) In toluene at 100℃; for 15h;
71% With Co(1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)<SUB>2</SUB>Cl<SUB>2</SUB>; potassium methanolate In tert-butyl methyl ether at 50℃; for 8h;
47% With C20H28Cl2CoFeNOP; potassium methanolate; methyllithium In tert-butyl methyl ether at 50℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube;
18% With potassium methanolate; [1,3-bis(2,4,6-trimethylphenyl)imidazol]-2-ylidene; zinc dibromide In tert-butyl methyl ether at 50℃; Green chemistry;
With catalyst: silica-SMAP/Pd(CH3COO)2; K(CH3COO) In benzene byproducts: 4,4'-bis(trifluoromethyl)biphenyl; soln. of Pd complex in benzene and aryl halide added to mixt. of silica-SMAP, B compd., and KOAc in degassed benzene in glass tube with stirrer,tube sealed with screw cap, removed from glove box, mixt. stirred at 60 °C for 10 h;
With potassium phosphate tribasic heptahydrate; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II); XPhos In ethanol at 20℃; for 2h;
> 99 %Chromat. With Ni2(1,3-dicyclohexylimidazolin-2-ylidene)4(μ-(η22)-1,5-cyclooctadiene); sodium acetate In methyl cyclohexane at 100℃; for 24h; Schlenk technique; Inert atmosphere;

Reference: [1]Lamola, Jairus L.; Moshapo, Paseka T.; Holzapfel, Cedric W.; Christopher Maumela, Munaka [Tetrahedron Letters, 2022, vol. 88]
[2]Location in patent: experimental part Chow, Wing Kin; Yuen, On Ying; So, Chau Ming; Wong, Wing Tak; Kwong, Fuk Yee [Journal of Organic Chemistry, 2012, vol. 77, # 7, p. 3543 - 3548]
[3]Qiao, Yusen; Yang, Qiaomu; Schelter, Eric J. [Angewandte Chemie - International Edition, 2018, vol. 57, # 34, p. 10999 - 11003][Angew. Chem., 2018, # 130, p. 11165 - 11169,5]
[4]Tian, Ya-Ming; Guo, Xiao-Ning; Krummenacher, Ivo; Wu, Zhu; Nitsch, Jörn; Braunschweig, Holger; Radius, Udo; Marder, Todd B. [Journal of the American Chemical Society, 2020, vol. 142, # 42, p. 18231 - 18242]
[5]Cai, Mingzhong; Luo, Chengkai; Xu, Caifeng; Huang, Bin [Synthesis, 2022, vol. 54, # 5, p. 1339 - 1346]
[6]Kawamorita, Soichiro; Ohmiya, Hirohisa; Iwai, Tomohiro; Sawamura, Masaya [Angewandte Chemie - International Edition, 2011, vol. 50, # 36, p. 8363 - 8366]
[7]Kawamorita, Soichiro; Ohmiya, Hirohisa; Iwai, Tomohiro; Sawamura, Masaya [Angewandte Chemie - International Edition, 2011, vol. 50, # 36, p. 8363 - 8366]
[8]Xu, Jinhui; Cao, Jilei; Wu, Xiangyang; Wang, Han; Yang, Xiaona; Tang, Xinxin; Toh, Ren Wei; Zhou, Rong; Yeow, Edwin K. L.; Wu, Jie [Journal of the American Chemical Society, 2021, vol. 143, # 33, p. 13266 - 13273]
[9]Kuehn, Laura; Huang, Mingming; Radius, Udo; Marder, Todd B. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 27, p. 6601 - 6606]
[10]Iwai, Tomohiro; Harada, Tomoya; Tanaka, Ryotaro; Sawamura, Masaya [Chemistry Letters, 2014, vol. 43, # 5, p. 584 - 586]
[11]Fuerstner, Alois; Seidel, Guenter [Organic Letters, 2002, vol. 4, # 4, p. 541 - 543]
[12]Yamamoto, Yutaro; Matsubara, Hiroshi; Yorimitsu, Hideki; Osuka, Atsuhiro [ChemCatChem, 2016, vol. 8, # 14, p. 2317 - 2320]
[13]Verma, Piyush Kumar; Mandal, Souvik; Geetharani [ACS Catalysis, 2018, vol. 8, # 5, p. 4049 - 4054]
[14]Yao, Wubing; Fang, Huaquan; Peng, Sihan; Wen, Huanan; Zhang, Lei; Hu, Aiguo; Huang, Zheng [Organometallics, 2016, vol. 35, # 10, p. 1559 - 1564]
[15]Bose, Shubhankar Kumar; Marder, Todd B. [Organic Letters, 2014, vol. 16, # 17, p. 4562 - 4565]
[16]Kawamorita, Soichiro; Ohmiya, Hirohisa; Iwai, Tomohiro; Sawamura, Masaya [Angewandte Chemie - International Edition, 2011, vol. 50, # 36, p. 8363 - 8366]
[17]Ji, Hong; Wu, Li-Yang; Cai, Jiang-Hong; Li, Guo-Rong; Gan, Na-Na; Wang, Zhao-Hua [RSC Advances, 2018, vol. 8, # 25, p. 13643 - 13648]
[18]Kuehn, Laura; Jammal, Dominik G.; Lubitz, Katharina; Marder, Todd B.; Radius, Udo [Chemistry - A European Journal, 2019, vol. 25, # 40, p. 9514 - 9521]
  • 4
  • [ 56634-50-5 ]
  • [ 214360-65-3 ]
  • 4-[4-(trifluoromethyl)phenyl]furan-2(5H)-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With tetra-(n-butyl)ammonium iodide; cesium fluoride In water; toluene for 24h; Heating / reflux; 1.3 Utilisation of cesium fluoride as base; A mixture containing 4-bromo-5(H)furanone (1.010 g, 6.198 mmol), 4-trifluoromethylphenylboronic acid (1.432 g, 7.540 mmol), trans- dichlorobis(triphenylphosphine)palladium (II) (0.216 g, 3.077XlO"1 mmol), tetrabutylammonium iodide (0.119 g, 3.222XlO"1 mmol) and cesium fluoride (4.681 g, 30.811 mmol) in toluene (30 mL) and water (30 mL) were gently refluxed for 24 h under nitrogen before the reaction mixture was allowed to cool to room temperature. Brine (50 mL) was added and the product extracted with ethyl acetate (3x50 mL). The organic fractions were combined, washed with brine (3x50 mL), dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give a brown solid. The resulting solid was chromatographed (silica gel: eluent 50:50 dichloromethane/light petroleum) to give 4-(4 '-trifluoromethylphenyl)furan-2(5H)-one 6 (1.211 g, 86%) as a pale yellow powder, (ref. PDS-2-97). UV- Vis λmax (MeOH) 209(16722), 260(20923) nm; 1H NMR (CDCl3) δ 7.75 (d, 2H, J= 8.3 Hz, H3', H5'), 7.63 (d, 2H, J= 8.3 Hz, H21, H6'), 6.48 (t, IH, J= 1.9 Hz, H3), 5.21 (d, 2H, J= 1.9 Hz, H5); 13C NMR (CDCl3, 75 MHz) δ 173.0 (C2), 162.0 (C4), 133.27 (q, J= 33.0 Hz, C4'), 132.95 (Cl1), 126.8 (C21, C6'), 126.3 (q, J = 3.6 Hz, C31, C51), 123.4 (q, J = 270.8 Hz, C4'-CF3), 115.5 (C3), 70.8 (C5); 19F NMR (CDCl3, 282 MHz) δ -63.54 (s, 3F, C4'-CF3); IR (KBr) 3094, 2941, 1794, 1759, 1626, 1615, 1577, 1439, 1418, 1325, 1247, 1160, 1113, 1070, 1049, 1016, 994, 891, 872, 844, 772, 748, 708, 692, 679, 601, 521, 438, 422 cm"1.
59% With potassium fluoride; tetra-(n-butyl)ammonium iodide In water; toluene for 24h; Heating / reflux; 1.3 Example 3; 4-(4 '-Trifluoromethylphenyl)furan-2(5H)-one 3; Utilization of potassium fluoride as base; A mixture containing 4-bromo-5(H)furanone (0.250 g, 1.534 mmol), pinacolato(4-trifluoromethylphenylboronic) ester (0.504 g, 1.852 mmol), trα«5-dichlorobis(triphenylphosphine)palladium (II) (0.054 g, 7.694xlO"2 mmol), tetrabutylammonium iodide (0.029 g, 7.85IxIO"2 mmol) and potassium fluoride (0.362 g, 6.231 mmol) in toluene (10 mL) and water (10 mL) were gently refluxed for 24 h under nitrogen before the reaction mixture was allowed to cool to room temperature. Brine (50 mL) was added and the product extracted with dichloromethane (3x20 mL). The organic fractions were combined, washed with brine (3x20 mL), dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give a dark brown solid. The resulting solid was chromatographed (silica gel: eluent 50:50 dichloromethane/light petroleum followed by 100% dichloromethane) to give 4-(4 '-trifluoromethylphenyl)furan- 2(5H)-one 3 (0.206 g, 59%) as a pale yellow powder, dec. 157-1580C (ref. PDS-1-63).
  • 5
  • [ 98-08-8 ]
  • 4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ No CAS ]
  • [ 325142-82-3 ]
  • [ 214360-65-3 ]
  • 6
  • [ 402-43-7 ]
  • [ 25015-63-8 ]
  • [ 98-08-8 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
82% With triethylamine In 1,4-dioxane at 80℃; for 6h;
53% With copper(l) iodide; iron(III)-acetylacetonate; N,N,N,N,-tetramethylethylenediamine; sodium hydride In tetrahydrofuran; mineral oil at -10℃; Inert atmosphere;
  • 7
  • [ 455-13-0 ]
  • [ 25015-63-8 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
Stage #1: With triethylamine In 1,4-dioxane at 80℃; for 18h; Stage #2: 4-Iodobenzotrifluoride; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In 1,4-dioxane at 80℃; for 18h; 53 4,4,5,5-Tetramethyl-2-[4-(trifluoromethyl)phenyl]-1,3,2-dioxaborolane [00371] In a reaction tube under nitrogen, a mixture of PdCl2(dppf)CH2Cl2 (21 mg; 0.026 mmol) and triethylamine (0.34 ml; 2.44 mmol) in dioxane (2.5 ml; dried over 4 A sieves) was sealed and stirred at 80 C. overnight (18 h). After cooling to room temperature, HB(pin) (0.19 ml; 1.31 mmol) was added followed by 4-iodobenzotrifluoride (235 mg; 0.864 mmol) in dioxane (2.5 ml; dried over 4 A sieves) and the reaction mixture was stirred at 80 C. GC analysis after 18 hours showed the desired borate compound at 5.0 minutes.
  • 8
  • [ 98-08-8 ]
  • [ 73183-34-3 ]
  • [ 1073339-21-5 ]
  • [ 325142-82-3 ]
  • [ 214360-65-3 ]
  • 9
  • [ 76-09-5 ]
  • [ 402-43-7 ]
  • [ 51901-85-0 ]
  • [ 7440-66-6 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
48% With 3-chloroprop-1-ene; trifluoroacetic acid In acetonitrile Zn dust (1.5 equiv., acid-activated) , CoBr2 (0.1 equiv.), stirred for 5min with allyl chloride (0.3 equiv.), a soln. of aryl halide (1 equiv.) and a soln. 1 equiv. of B compd. added at room temp., stirred for 30 mi n, tranesterificated with pinacol; hydrolized (NH4Cl), extd. (diethyl ether);
  • 10
  • [ 402-43-7 ]
  • [ 73183-34-3 ]
  • [ 94647-81-1 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
65% With copper(l) iodide; tributylphosphine; potassium <i>tert</i>-butylate In tetrahydrofuran byproducts: KBr; react. of (B(OC(CH3)2)2)2 (1.5 equiv.), 4-CF3C6H4Br (1 equiv.), CuI (10 mol%), nBu3P (13 mol%) and KOtBu (1.5 equiv.) at room temp.;
  • 11
  • [ 455-13-0 ]
  • [ 73183-34-3 ]
  • [ 94647-81-1 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
69% With copper(l) iodide; tributylphosphine; potassium <i>tert</i>-butylate In tetrahydrofuran byproducts: KI; react. of (B(OC(CH3)2)2)2 (1.5 equiv.), 4-CF3C6H4I (1 equiv.), CuI (10 mol%), nBu3P (13 mol%) and KOtBu (1.5 equiv.) at room temp.;
  • 12
  • [ 455-13-0 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
92% Stage #1: bis(pinacol)diborane With diethylzinc; sodium t-butanolate In tetrahydrofuran; hexane at 0 - 20℃; for 0.5h; Schlenk technique; Glovebox; Inert atmosphere; Stage #2: 4-Iodobenzotrifluoride In tetrahydrofuran; hexane at 20 - 75℃; for 24h; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube;
86% With 10H-phenothiazine; caesium carbonate In acetonitrile for 24h; Irradiation; Sealed tube; Inert atmosphere;
80% With potassium methanolate; [1,3-bis(2,4,6-trimethylphenyl)imidazol]-2-ylidene; zinc dibromide In tert-butyl methyl ether at 20℃; for 8h; Inert atmosphere; Glovebox; Schlenk technique; Green chemistry;
79% With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; XPhos In toluene at 120℃; III.1 1. Sub3-1 Synthesis Example Put 1-Iodo-4-(trifluoromethyl)benzene (5.0 g, 18.4 mmol) in a round-bottom flask, Bis(pinacolato)diboron (4.9 g, 19.3 mmol), Pd2(dba)3 (0.51 g, 0.55 mmol) , x-phos (0.53 g, 1.10 mmol), KOAc (3.6 g, 36.8 mmol) and Toluene (61 mL) were added and refluxed at 120 °C. After the reaction was completed, the reaction solution was concentrated and separated through a silica gel column to obtain 3.9 g (yield: 79%) of the product.
73% With pyridine; cesium fluoride In dimethyl sulfoxide at 105℃; for 2h; Inert atmosphere; Schlenk technique; For Liquid Aryl Iodides; General Procedure B General procedure: An oven-dried Schlenk tube, containing a Teflon-coated magnetic stir bar was charged with CsF (228 mg, 1.5 mmol, 3 equiv) and bispinacolatodiboron (254 mg, 1 mmol, 2 equiv). Under an argon atmosphere, freshly distilled DMSO (0.4 mL), the appropriate aryl iodide (0.5mmol), and pyridine (0.4 to 1 equiv) were added successively. The reaction mixture was heated to 105 °C and stirred for 2 h under argon.
71% With bis-(dimethylamino)methane In water; acetone; acetonitrile at -5℃; for 0.25h; UV-irradiation; Flow reactor; chemoselective reaction;
70% With lithium tert-butoxide In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; Schlenk technique;
69% With copper(l) iodide; tributyl-amine; potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃;
66% With copper(l) iodide; palladium diacetate; caesium carbonate; triphenylphosphine In acetonitrile at 20℃; for 24h; chemoselective reaction;
61% With silver fluoride In acetonitrile at 20℃; Sealed tube; UV-irradiation; Inert atmosphere; 2.3. General procedure for the photo-driven reactions General procedure: To a 10 mL Pyrex reaction vial were added 20 mg of organichalide, 2.5 eq of B2pin2, 20 mg of silver(I) salt and 2.0 mL of MeCN. n-C12H26 was added as an internal standard of GC as necessary. Thevial was sealed with a butyl rubber stopper and then purged withN2. The vial was half immersed in a water bath to maintain roomtemperature and irradiated from the side. After every certain interval,ca. 1.0 μL of the solution was withdrawn and analysed with GCor GC-MS to check the products and the reaction kinetics. To isolatethe products, the dispersion was filtered with celite and thenthe filtrate was purified by column chromatography. For thegram-scale reaction, 1.0 g of 1, 2.5 eq of B2pin2 and 1.0 g of AgFwere dispersed in 60 mL of MeCN. The reaction was performedon the building roof for sunlight irradiation from 10:00 to 15:00.The ambient temperature was 25 - 35 °C.
51% With p-phenylpyridine; potassium methanolate In tert-butyl methyl ether at 85℃; for 12h; Sealed tube;
42% With 3,7-di([1,1'-biphenyl]-4-yl)-10-(4-(trifluoromethyl)phenyl)-10H-phenoxazine; 1,8-diazabicyclo[5.4.0]undec-7-ene In dimethyl sulfoxide at 20℃; for 12h; Inert atmosphere; Irradiation; chemoselective reaction;
40% Stage #1: bis(pinacol)diborane With potassium ethoxide; C40H62N4Zn2 In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Glovebox; Schlenk technique; Stage #2: 4-Iodobenzotrifluoride In tetrahydrofuran at 75℃; for 12h; Inert atmosphere; Glovebox; Schlenk technique;
31% With 1,10-Phenanthroline; potassium <i>tert</i>-butylate In dimethyl sulfoxide; toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;
81 %Chromat. With copper(II) ferrite; potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 20℃; for 12h; Green chemistry; 2.2. General procedure for borylation of iodoarenes General procedure: 4-Iodoanisole (0.813 mmol, 200 mg), bis(pinacolato)diboron (1.219 mmol, 309 mg) were dissolved in 3 mL of dmf followed by copper ferrite nanoparticles (5mol% with respect to 4-iodoanisole) and potassiumtert-butoxide (1.219 mmol, 137 mg) were added to a 10 mLcapped vial and stirred at RT for time indicated. After stirring, the mixture was diluted with diethyl ether and filtered through celite bed. The filtrate was extracted with water (3 times) and the organic phase was dried over anhydrous MgSO4. The crude product was subjected to analyze by GC-MS. The conversion yield is accurately measured based on the consumption of 4-iodoanisole and the side product formed due to protodeiodination.
75 %Spectr. With Co(1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)<SUB>2</SUB>Cl<SUB>2</SUB>; potassium methanolate In tert-butyl methyl ether at 50℃; for 8h;

Reference: [1]Nagashima, Yuki; Takita, Ryo; Yoshida, Kengo; Hirano, Keiichi; Uchiyama, Masanobu [Journal of the American Chemical Society, 2013, vol. 135, # 50, p. 18730 - 18733]
[2]Arman, Hadi D.; Dang, Hang. T.; Haug, Graham C.; He, Ru; Jin, Shengfei; Larionov, Oleg V.; Nguyen, Viet D.; Nguyen, Vu T.; Schanze, Kirk S. [Journal of the American Chemical Society, 2020]
[3]Bose, Shubhankar Kumar; Marder, Todd B. [Organic Letters, 2014, vol. 16, # 17, p. 4562 - 4565]
[4]- KR102324529, 2021, B1 Location in patent: Paragraph 0455-0458
[5]Pinet, Sandra; Liautard, Virginie; Debiais, Mégane; Pucheault, Mathieu [Synthesis, 2017, vol. 49, # 21, p. 4759 - 4768]
[6]Chen, Kai; Zhang, Shuai; He, Pei; Li, Pengfei [Chemical Science, 2016, vol. 7, # 6, p. 3676 - 3680]
[7]Cid, M. B.; Díaz, Cristina; Franco, Mario; Lamsabhi, Al Mokhtar; Sainz, Raquel; Tortosa, Mariola [Catalysis science and technology, 2021, vol. 11, # 10, p. 3501 - 3513]
[8]Kleeberg, Christian; Dang, Li; Lin, Zhenyang; Marder, Todd B. [Angewandte Chemie - International Edition, 2009, vol. 48, p. 5350 - 5354][Angew. Chem., Int. Ed., 2009, vol. 121, p. 5454 - 5458]
[9]Ratniyom, Jadsada; Dechnarong, Nattanee; Yotphan, Sirilata; Kiatisevi, Supavadee [European Journal of Organic Chemistry, 2014, vol. 2014, # 7, p. 1381 - 1385] Ratniyom, Jadsada; Dechnarong, Nattanee; Yotphan, Sirilata; Kiatisevi, Supavadee [European Journal of Organic Chemistry, 2014, vol. 2014, # 7, p. 1381 - 1385]
[10]Cui, Enxin; Qiao, Dan; Li, Haibin; Guo, Lirong; Tung, Chen-Ho; Wang, Yifeng [Journal of Catalysis, 2021, vol. 402, p. 255 - 263]
[11]Zhang, Li; Jiao, Lei [Journal of the American Chemical Society, 2017, vol. 139, # 2, p. 607 - 610]
[12]Lee, Da Seul; Kim, Chung Soo; Iqbal, Naila; Park, Gyeong Su; Son, Kyung-Sun; Cho, Eun Jin [Organic Letters, 2019, vol. 21, # 24, p. 9950 - 9953]
[13]Li, Yafei; Dang, Yan; Li, Dawei; Pan, Huifen; Zhang, Liang; Wang, Li; Cao, Zhu; Li, Yahong [Organometallics, 2021, vol. 40, # 4, p. 482 - 489]
[14]Niu, Yi-Jie; Sui, Guo-Hui; Zheng, Hong-Xing; Shan, Xiang-Huan; Tie, Lin; Fu, Jia-Le; Qu, Jian-Ping; Kang, Yan-Biao [Journal of Organic Chemistry, 2019, vol. 84, # 17, p. 10805 - 10813]
[15]Mohan, Balaji; Kang, Hyuntae; Park, Kang Hyun [Catalysis Communications, 2016, vol. 85, p. 61 - 65]
[16]Verma, Piyush Kumar; Mandal, Souvik; Geetharani [ACS Catalysis, 2018, vol. 8, # 5, p. 4049 - 4054]
  • 13
  • [ 98-08-8 ]
  • [ 73183-34-3 ]
  • [ 1197374-02-9 ]
  • [ 325142-82-3 ]
  • [ 214360-65-3 ]
  • 14
  • [ 98-56-6 ]
  • [ 25015-63-8 ]
  • [ 98-08-8 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
84% With tetra-(n-butyl)ammonium iodide; triethylamine; bis(dibenzylideneacetone)-palladium(0); 2,2'-bis(di-tert-butylphosphino)diphenyl ether In 1,4-dioxane at 100℃; for 24h;
  • 15
  • [ 455-14-1 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
86% With tert.-butylnitrite; eosin In acetonitrile at 20℃; for 2h; Irradiation; General experimental procedure for the synthesis of aryl and hetero-aryl boronates.representative procedure for the synthesis of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: General procedure: tert-Butyl nitrite (155 mg, 1.1 mmol) wasadded drop wise to a mixture of bis(pinacolato)diborane (127 mg, 0.5 mmol),4-anisidine (61 mg, 0.5 mmol) and eosin Y (0.01 mmol) in acetonitrile (3 mL).The resulting mixture was stirred at room temperature under irradiation withblue LED for 2 h (TLC). This mixture after being diluted with ethyl acetate(5 mL) was ltered through celite and the ltrate was extracted with ethylacetate (3 10 mL). The extract was washed with brine, dried over anhydrousNa 2 SO 4 , and evaporated to leave the crude product which was puried bycolumn chromatography over silica gel with hexane-ethyl acetate (98:2) aseluent to furnish pure 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as a light yellow viscous liquid (3d, 208 mg, 88%); IR (neat)2978, 2933, 2839, 2526, 2050, 1950, 1911, 1724, 1605, 1570 cm1;1H NMR(500 MHz, CDCl 3 ) d 1.33 (s, 12H), 7.82 (s, 3H), 6.89 (d, J = 8.0 Hz, 2H), 7.75 (d,J = 8.0 Hz, 2H);13C NMR (125 MHz, CDCl 3 ) d 24.9 (4C), 55.2, 83.6 (2C), 113.4(2C), 136.6 (2C), 162.3. The spectroscopic data is in full agreement with thosereported for an authentic sample.14This procedure was followed for all thereactions listed in Table 2. All of these products (3a,143b,143c,16a3d,143e,143f,8a3g,143h,143i,143j,8a3k,8a3l,8a3m,143n,8c3o,16b) are known compounds,and their spectroscopic data are in agreement with those previously reported.
75% With tert.-butylnitrite; dibenzoyl peroxide In acetonitrile at 20℃; for 2h;
75% With tert-butyl nitrite; benzoyl peroxide In acetonitrile MeCN, CF3C6H4NH2 (1 mmol) and tBuONO (1.5 mmol) added to B2pin2 (1 mmol)and benzoyl peroxide (0.02 mmol), mixt. stirred at room temp. for 2 h; soln. concd. (under reduced pressure), residue chromd.;
73% Stage #1: 4-trifluoromethylphenylamine With fluoroboric acid; sodium nitrite In water at 0℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: bis(pinacol)diborane With methanol at 22 - 25℃; for 36h; Inert atmosphere; Schlenk technique; Sealed tube; Synthesis of aryldiazonium tetrafluoroborates General procedure: An arylamine (50 mmol) was dissolved in 50% hydrofluoroboric acid(17 mL) and water (20 mL). After cooling the reaction mixture to 0 °C, a solution of sodium nitrite (3.4 g in 7.5 mL water) was added dropwise to the reaction system (over 5 min). The resulting mixture was stirred for 1h and the precipitate was collected by filtration. It was redissolved in the minimum amount of acetone and then diethyl ether was added to precipitate the aryl diazonium tetrafluoroborate. The product was filtered, washed with diethyl ether and dried under reduced pressure. Borylation of aryldiazonium salts; general procedure The aryldiazonium salt (0.5 mmol) and (Bpin)2 (0.75 mmol) were added to an oven-dried Schlenk tube. The tube was evacuated and backfilled with argon (three times). CH3OH (0.8 mL) was added to this Schlenk tube. The tube was sealed and the mixture was stirred at room temperature (22-25 °C) for 36 h. After evaporation of the solvent, the residue was purified by column chromatography to afford the product.The arylboronates were purified by chromatography on a silica column eluting with petroleum ether (boiling range 60-90 °C) or a petroleumether/ethyl acetate mixture (ca. 60:1) by volume giving Rf values for the boronates of ca. 0.2-0.3.
68% Stage #1: 4-trifluoromethylphenylamine With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: With sodium tetrafluoroborate In water at 5℃; Stage #3: bis(pinacol)diborane With copper(I) bromide In water; acetonitrile at 20℃; for 3h;
60% Stage #1: 4-trifluoromethylphenylamine With tetrafluoroboric acid; sodium nitrite In water at 0℃; for 1h; Stage #2: bis(pinacol)diborane In water; acetone at 20℃; Sealed tube; General procedure for the preparation of aryl diazonium tetrafluoroborates General procedure: Aryl amine (10 mmol) was dissolved in a mixture of 5 mL of distilled water and 3.4 mL of 50% hydrofluoroboric acid. After cooling the reaction mixture to 0 °C using ice bath and the sodium nitrite (0.69 g in 2 mL distilled water), was added dropwise in 5 min interval of time. The resulting mixture was stirred for 1 h and the precipitate was collected by filtration and redissolved in minimum amount of acetone. Diethylether was added until precipitation of aryl diazonium tetrafluoroborate, which is filtered, washed several times with diethyl ether and dried under vacuum. Typical reaction procedure: General procedure: Diazonium tetrafluoroborate salts (0.5 mmol) and B2pin2 (1.5 mmol) were transferred into an oven-dried tube under air. Then acetone/H2O (2/1, 4 mL) were added into the tube via syringe. The sealed tube was keep at 20 °C and stirred for 1-2 h. After the reaction was complete, dichloromethane was added to extract the product and the combined organic solution was dried by Na2SO4. The pure product was isolated after column chromatography on silica gel (petroleum ether/ethyl acetate).
48 %Spectr. With air In 1,4-dioxane at 20℃; for 48h; Irradiation;

  • 16
  • [ 61676-62-8 ]
  • [ 402-43-7 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
99% With n-butyllithium; Triisopropyl borate In tetrahydrofuran; hexane at -60℃; for 5h;
96% Stage #1: p-trifluoromethylphenyl bromide With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78℃; Inert atmosphere;
83% With n-butyllithium In tetrahydrofuran; hexane at -60℃; Flow reactor;
73% Stage #1: p-trifluoromethylphenyl bromide With n-butyllithium In diethyl ether; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In diethyl ether; hexane at -78 - 20℃; for 12h; 1-2 (1-2) Synthesis of 2-[4-(trifluoromethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Compound L1-2) 4-bromobenzotrifluoride (4.8 g, 21.3 mmol) was placed in a reaction flask. To ensure a nitrogen atmosphere in the reaction flask, the gas in the reaction flask was drawn out and the reaction flask was refilled with nitrogen gas in a rapid manner three times. To the reaction flask, 50 ml of anhydrous diethylether was added, and then 10 ml of n-butyllithium solution (25.6 mmol, 2.5 M in n-hexane) was slowly added at -78° C. to obtain a mixture. In the meanwhile, the color of the mixture changed from transparent to cloudy green. The mixture was kept at -78° C. and continuously stirred for 60 minutes. Next, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.2 ml, 25.6 mmol) was slowly added to the mixture at -78° C., and then the temperature was slowly raised to and kept at 20° C. for 12 hours for reaction. The color of the mixture in the reaction flask changed from cloudy green to cloudy white. Deionized water was slowly added to the mixture to terminate the reaction in the reaction flask. The solvents in the mixture were drawn out of the reaction flask, and the residue in the reaction flask was washed several times with ethyl acetate and with a saturated sodium chloride solution to collect an organic layer, followed by dehydration of the organic layer using sodium sulfate (Na2SO4) to thereby obtain a crude product. The crude product was recrystallized in a mixed solvent having dichloromethane and n-hexane (dichloromethane:n-hexane=1:1) at 20° C., thereby obtaining white crystals (4.27 g, 73% yield). (0049) The spectrum analysis for the white crystals is: 1H NMR (400 MHz, CDCl3): δ 7.88 (d, J=8.0, 2H), 7.59 (d, J=8.0 Hz, 2H), 1.33 (s, 12H); 19F NMR (376 MHz, CDCl3, 298K): δ -63.06(s). The white crystals were confirmed to be Compound L1-2 having a chemical structure represented by
Stage #1: p-trifluoromethylphenyl bromide With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran

  • 17
  • [ 37658-00-7 ]
  • [ 214360-65-3 ]
  • [ 1234215-27-0 ]
YieldReaction ConditionsOperation in experiment
75% Stage #1: 4-trifluoromethylphenylboronic acid pinacol ester With sodium tert-pentoxide In 1,4-dioxane for 0.166667h; Inert atmosphere; Glove box; Stage #2: With (t-butoxy)[1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)-2H-imidazol-2-ylidene]-copper In 1,4-dioxane at 20℃; for 0.166667h; Inert atmosphere; Glove box; Stage #3: (E)-1-chloro-2-hexene In 1,4-dioxane at 45℃; for 24h; Inert atmosphere; Glove box; regioselective reaction;
  • 18
  • [ 402-43-7 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
95% Stage #1: bis(pinacol)diborane With diethylzinc; sodium t-butanolate In tetrahydrofuran; hexane at 0 - 20℃; for 0.5h; Schlenk technique; Glovebox; Inert atmosphere; Stage #2: p-trifluoromethylphenyl bromide In tetrahydrofuran; hexane at 20 - 120℃; for 24h; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube;
92% With C26H25Cl2FeN2PPd; potassium acetate In isopropyl alcohol at 85℃; for 6h; Schlenk technique; Inert atmosphere;
78% With fac-tris(2-phenylpyridinato-N,C2')iridium(III); tributyl-amine; water In acetonitrile at 25℃; for 36h; Schlenk technique; Inert atmosphere; Sealed tube; Irradiation;
76% With C37H51ClFeNPPd; potassium acetate In 1,4-dioxane at 80℃; for 3h; Inert atmosphere;
65% With potassium methanolate; [1,3-bis(2,4,6-trimethylphenyl)imidazol]-2-ylidene; zinc dibromide In tert-butyl methyl ether at 20℃; Green chemistry;
64% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In dimethyl sulfoxide at 80℃; for 48h; Inert atmosphere;
61% With sodium methylate In N,N-dimethyl acetamide at 60℃; for 6h; Inert atmosphere; Schlenk technique;
52% With p-phenylpyridine; potassium methanolate In tert-butyl methyl ether at 85℃; for 12h; Sealed tube;
46% With bis-(dimethylamino)methane In water; acetone; acetonitrile at -5℃; for 0.5h; UV-irradiation; Flow reactor; chemoselective reaction;
With (C5H5FeC5H3C(CH3)NC6H4CH3)PdCl(tricyclohexylphosphine); potassium acetate In 1,4-dioxane at 100℃; for 2h; Inert atmosphere;
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 110℃; for 0.166667h; Microwave irradiation; 4,4,5,5-Tetramethyl-2-phenyl-1,3,2-dioxaborolane General procedure: To 2 mL of 1,4-dioxane in microwave reaction vessel were added bromobenzene (0.20 g, 1.27 mmol), bis(pinacolato)diboron (0.36 g, 1.40 mmol), potassium acetate (0.38 g, 3.8 mmol), and PdCl2(dppf) (0.028 g, 0.038 mmol). The reaction mixture was heated to 110 °C by microwave irradiation at power 100 W for 10 min. After solvent was removed under reduced pressure, the residue was purified by dry column vacuum chromatography (DCVC) using dichloromethane (DCM) as eluent provided the 0.16 g in 62 % yield;
72 %Spectr. With bis-triphenylphosphine-palladium(II) chloride; potassium acetate In neat (no solvent) at 110℃; for 24h; 3.1. Miyaura borylation General procedure: Under atmospheric conditions, a 10-mL screwcap vial equipped with a magnetic stir bar was charged with Pd source (0.01 mmol, 0.02 equiv), base (0.6 mmol, 1.2 equiv), bis(pinacolato)diboron (0.525 mmol, 1.05 equiv) and aryl halide (0.5 mmol, 1 equiv). The reaction vial was transferred to a preheated oil bath. The reaction was stirred at 110 °C for the desired time to give a grey mixture. The reaction mixture was extracted with 10 mL of ethyl acetate, washed with water (2 × 15 mL), brine (10 mL), and dried over Na2SO4. The solvent was evaporated in vacuo to afford the crude product. The product yield was determined by GC-FID based on integration relative to hexamethylbenzene as an internal standard. The residue was purified by column chromatography on silica gel (eluting with 5:95 ethyl acetate in hexane) to give pure aryl boronic ester.

Reference: [1]Nagashima, Yuki; Takita, Ryo; Yoshida, Kengo; Hirano, Keiichi; Uchiyama, Masanobu [Journal of the American Chemical Society, 2013, vol. 135, # 50, p. 18730 - 18733]
[2]Škoch, Karel; Schulz, Jiří; Císařová, Ivana; Štěpnička, Petr [Organometallics, 2019, vol. 38, # 15, p. 3060 - 3073]
[3]Jiang, Min; Yang, Haijun; Fu, Hua [Organic Letters, 2016, vol. 18, # 20, p. 5248 - 5251]
[4]Location in patent: experimental part Wang, Lianhui; Li, Jingya; Cui, Xiuling; Wu, Yusheng; Zhu, Zhiwu; Wu, Yangjie [Advanced Synthesis and Catalysis, 2010, vol. 352, # 11-12, p. 2002 - 2010]
[5]Bose, Shubhankar Kumar; Marder, Todd B. [Organic Letters, 2014, vol. 16, # 17, p. 4562 - 4565]
[6]Liu, Cham-Chuen; Liu, Qian; Yiu, Shek-Man; Chan, Michael C. W. [Organometallics, 2019, vol. 38, # 15, p. 2963 - 2971]
[7]Cid, M. B.; Díaz, Cristina; Franco, Mario; Lamsabhi, Al Mokhtar; Sainz, Raquel; Tortosa, Mariola [Catalysis science and technology, 2021, vol. 11, # 10, p. 3501 - 3513]
[8]Zhang, Li; Jiao, Lei [Journal of the American Chemical Society, 2017, vol. 139, # 2, p. 607 - 610]
[9]Chen, Kai; Zhang, Shuai; He, Pei; Li, Pengfei [Chemical Science, 2016, vol. 7, # 6, p. 3676 - 3680]
[10]Location in patent: experimental part Wang, Lianhui; Cui, Xiuling; Li, Jingya; Wu, Yusheng; Zhu, Zhiwu; Wu, Yangjie [European Journal of Organic Chemistry, 2012, # 3, p. 595 - 603]
[11]More, Kunal N.; Hong, Victor S.; Lee, Ahyeon; Park, Jongsung; Kim, Shin; Lee, Jinho [Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 14, p. 2513 - 2517]
[12]Boontiem, Phongsakorn; Kiatisevi, Supavadee [Inorganica Chimica Acta, 2020, vol. 506]
  • 19
  • [ 77-85-0 ]
  • [ 214360-65-3 ]
  • Na(4-(CF3)C6H4B(OCH2)3CCH3) [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With sodium hydroxide In 1,4-dioxane; water at 30℃; for 16h; Inert atmosphere;
  • 20
  • [ 98-56-6 ]
  • [ 73183-34-3 ]
  • [ 433-19-2 ]
  • [ 214360-65-3 ]
  • 21
  • [ 132803-38-4 ]
  • [ 25015-63-8 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
85% With Et3N; tetrabutylammonium iodide In 1,4-dioxane 100°C, 24 h; GC;
85% With 1,1'-bis(di-tertbutylphosphino)ferrocene; tetra-(n-butyl)ammonium iodide; triethylamine; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane at 100℃; for 24h; Inert atmosphere;
  • 22
  • [ 25015-63-8 ]
  • [ 345958-72-7 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
83% With Et3N; tetrabutylammonium iodide In 1,4-dioxane 100°C, 24 h; GC;
83% With 1,1'-bis(di-tertbutylphosphino)ferrocene; tetra-(n-butyl)ammonium iodide; triethylamine; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane at 100℃; for 24h; Inert atmosphere;
  • 23
  • [ 1352285-38-1 ]
  • [ 214360-65-3 ]
  • (R)-2-methyl-5-(4-trifluoromethylphenyl)octa-3,4-diene [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With [1,3-bis(cyclohexyl)imidazol-2-ylidene]copper(I) chloride; sodium tert-pentoxide In 2,2,4-trimethylpentane at 60℃; for 24h; Inert atmosphere; optical yield given as %ee; stereoselective reaction;
  • 24
  • [ 104-92-7 ]
  • [ 214360-65-3 ]
  • [ 10355-12-1 ]
YieldReaction ConditionsOperation in experiment
87% With potassium phosphate; (C5H5FeC5H3C(CH3)NC6H4CH3)PdCl(tricyclohexylphosphine); potassium acetate In 1,4-dioxane; water at 100℃; for 3h; Inert atmosphere;
  • 25
  • [ 1377503-11-1 ]
  • [ 214360-65-3 ]
  • [ 1377503-27-9 ]
YieldReaction ConditionsOperation in experiment
72% With N-ethyl-N,N-diisopropylamine In 1,4-dioxane; water at 100℃; for 16h; Inert atmosphere; 50.1 Example 50: Preparation of (S)-2-(tert-butoxy)-2-(2-methyl-4-i4-(trif.uoromet vi¾phenvi)-5,6,7,8-Step 1 : (S)-methyl 2-(tert-butoxy)-2-(2-methvM-(4-(trifluoromethyl)phenyl)-5,6,7.8-2-(4-(Trifluoromethyl)phenyl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (115 g, 0.42 mmol), A/-ethyl-/V- isopropylpropan-2 -amine (120 μΙ_, 0.64 mmol) and water (500 μΙ.) were added to a stirred solution of (S)- methyl 2-(tert-butoxy)-2-(4-iodo-2-methyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-b]pyridin-3-yl)acetate (100 mg, 0.21 mmol) in dioxane (2 mL) in a reaction tube. The reaction mixture was degassed with argon for 2 minutes, then tetrakis(triphenylphosphine)palladium(0) (25 mg, 21 pmmol) was added and the vessel was sealed and heated at 100 °C for 16 hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate (30 mL) and water (30 mL) and the mixture was passed through a pad of celite. The layers of the filtrate were separated and the organic layer was washed with brine (30 mL), dried (MgS04) and concentrated in vacuo to yield the crude product as a brown gum. The residue was purified by flash column chromatography eluting with ethyl acetate in heptane (10%) to give the title compound (75 mg, 72%) as a yellow oil. 1H NMR (400 MHz, CDCI3) δ = 0.96 (s, 9H), 1.85-1.35 (m, 6H), 2.72 (s, 3H), 2.85-2.75 (m, 2H), 3.69 (s, 3H), 4.91 (s, 1 H), 7.40 (d, 1 H), 7.61 (d, 1 H), 7.71 (m, 2H). LCMS (run time = 5 minutes, basic): Rt = 3.64 minutes; m/z 492.06 [M+H+].
  • 27
  • [ 76-09-5 ]
  • [ 128796-39-4 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
83% In tetrahydrofuran at 20℃; for 12h; Molecular sieve;
In diethyl ether at 20℃; Inert atmosphere; Molecular sieve;
With magnesium sulfate In dichloromethane at 20℃; Glovebox; Schlenk technique; Inert atmosphere;
  • 28
  • [ 214360-65-3 ]
  • [ 402-44-8 ]
YieldReaction ConditionsOperation in experiment
68% With 1-fluoro-2,4,6-trimethylpyridinium hexafluorophosphate; (tBuCN)2Cu*OTf; silver fluoride; In tetrahydrofuran; at 80℃; for 18h;Inert atmosphere; General procedure: To an oven-dried 4 mL vial was added AgF (25 mg, 0.2 mmol, 2.0 equiv), ('BuCN^CuOTf (76 mg, 0.2 mmol, 2.0 equiv), [Me3pyF]PF6 (86 mg, 0.3 mmol, 3.0 equiv) and THF (2.0 mL). The aryl boronate ester (0.1 mmol, 1.0 equiv) was added (solid aryl boronate esters were weighed in the vial prior to adding THF, and liquid aryl boronate esters were added neat by syringe after the addition of THF). The vial was sealed with a Teflon- lined cap and heated at 50 °C with vigorous stirring for 18 h. The solution was allowed to cool to room temperature, and 11.0 mu^ (0.1 mmol, 1.0 equiv) of 1 -bromo-4-fluorobenzene was added as an internal standard. The crude reaction mixture was analyzed by 19F NMR spectroscopy to determine the yield of aryl fluoride. 19F NMR chemical shifts were compared to authentic samples of the aryl fluoride product to confirm the identity of the product, and the identities of the products were further assessed by GC/MS.; cReactions were conducted at 80 °C.
  • 29
  • trifluoromethylsilver [ No CAS ]
  • [ 214360-73-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
62% Stage #1: 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline With hydrogenchloride In water at 0℃; for 0.0833333h; Inert atmosphere; Schlenk technique; Stage #2: With tert.-butylnitrite at 0℃; for 0.25h; Inert atmosphere; Schlenk technique; Stage #3: trifluoromethylsilver at -78 - 20℃; for 4h; Inert atmosphere; Schlenk technique;
62% Stage #1: 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline With hydrogenchloride In water at 0℃; for 0.0833333h; Schlenk technique; Stage #2: With tert.-butylnitrite In water at -196 - 20℃; Schlenk technique; Inert atmosphere; Stage #3: trifluoromethylsilver In water at -78 - 20℃; for 5h; Schlenk technique; Inert atmosphere; Trifluoromethylation Procedure 1 (Table 1); General Procedure General procedure: An oven-dried Schlenk tube (A) equipped with a magnetic stir bar was charged with AgF (132.2 mg, 1.05 mmol, 3.5 equiv), sealed with a septum, and degassed by alternating vacuum evacuation and nitrogen backfill (three times) before freshly distilled EtCN (3 mL)was added. To the resulting suspension, which was precooled to -78 °C (dry ice-acetone bath), was added TMSCF3 (149.3 mg, 1.05 mmol, 3.5 equiv) by microsyringe. The mixture was allowed towarm to r.t. and stirring was continued for an additional 15 min. In due course, AgF solid dissolved and a gray, dark solution of [Ag-CF3] formed. Another Schlenk tube (B) equipped with a magnetic stir bar was charged with the aniline (ArNH2; 0.30 mmol, 1.0 equiv) in freshly distilled EtCN (1.5 mL). To the resulting solution, which was precooled to 0 °C (ice bath), aq HCl (12 M; 50.0 μL, 0.60mmol, 2.0 equiv) was added; precipitate formed immediately. After 5 min stirring, t-BuONO (37.7 mg, 0.33 mmol, 1.1 equiv) was added by microsyringe, and the mixture was allowed to stir at 0 °C for 15 min. The resulting suspension in Schlenk tube (B) was degassed by alternating vacuum evacuation at -196 °C (liquid nitrogen), then the solution was allowed to warm to r.t. under a nitrogen atmosphere (three times), and finally cooled to -78 °C (dry ice-acetone bath). The gray, dark solution of [AgCF3] in Schlenk tube (A), which was precooled to -78 °C (dry ice-acetone bath), was added to Schlenk tube (B) (ArN2+Cl-) by syringe at -78 °C (dry ice-acetone bath) over a period of 1 h. After the addition was complete, the reaction mixture was stirred for 3 h at -78 °C (dry ice-acetone bath), allowed to warm to r.t., and stirring was continued for an additional 1 h. An off-white precipitate was observed, and the reaction mixture was diluted with EtOAc (3 mL) and filtered through a short silica gel column. The solvent was removed under reduced pressure with a rotatory evaporator, and the crude residue was purified by silica gel column chromatography to give the desired trifluoromethylation product 3. The yields of products 3a, 3f, 3g, 3l, 3o, 3r, 3x, and 3zb are based on the 19F NMR spectra with 4-F3COC6H4OMe as internal standard. Analytical data for the representative product ethyl 4-(trifluoromethyl)benzoate (3i) are provided below. Data for other products can be found in the literature.
  • 30
  • [ 1377432-78-4 ]
  • [ 214360-65-3 ]
  • 7-methyl-2-(4-trifluoromethylphenyl)-3,7-dihydropyrrolo[2,3-d]pyrimidin-4-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
30% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water at 150℃; for 0.133333h; Sealed tube; Microwave irradiation; 38 Example 38 7-Methyl-2-(4-trifluoromethyl-phenyl)-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one A microwave reaction vial was charged with 2-chloro-7-methyl-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one (Intermediate A) (60 mg, 0.32 mmol), 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (107 mg, 0.39 mmol), tetrakis(triphenylphosphine)palladium(0) (18.9 mg, 0.01 mmol), and a 2M aqueous sodium carbonate solution (0.49 mL) in ethanol (2 mL). The vial was capped and heated in the microwave at 150° C. for 8 min. The resulting mixture was filtered through a pad of Celite and concentrated in vacuo. Flash chromatography (30/1 methylene chloride/methanol) afforded 7-methyl-2-(4-trifluoromethyl-phenyl)-3,7-dihydro-pyrrolo[2,3,-d]pyrimidin-4-one (29 mg, 30%) as a white solid. LC-MS calcd. for C14H11F3N3O [(M+H)+] 294, obsd. 294.0.
  • 31
  • 2-chloro-3,7-dihydro-4H-pyrrolo[2,3-d]pyrimidin-4-one [ No CAS ]
  • [ 214360-65-3 ]
  • 2-(4-trifluoromethylphenyl)-3,7-dihydropyrrolo[2,3-d]pyrimidin-4-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
3.8% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water at 150℃; for 0.166667h; Sealed tube; Microwave irradiation; 37 Example 37 2-(4-Trifluoromethylphenyl)-3,7-dihydropyrrolo[2,3-d]pyrimidin-4-one A microwave reaction vial was charged with 2-chloro-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one (Intermediate F) (80 mg, 0.32 mmol), 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (154 mg, 0.56 mmol), tetrakis(triphenylphosphine)palladium(0) (27.3 mg, 0.024 mmol) and a 2M aqueous sodium carbonate solution (0.75 mL) in ethanol (3 mL). The vial was sealed and the reaction was heated in the microwave at 150° C. for 10 min. At this time, the resulting mixture was filtered through a pad of Celite and concentrated in vacuo. Flash chromatography (30/1 methylene chloride/methanol) afforded 2-(4-trifluoromethyl-phenyl)-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one (5.0 mg, 3.8%) as a white solid. 1HNMR (400 MHz, DMSO-d6) δ ppm 6.50-6.59 (m, 1H) 7.9 (d, 2H) 7.11-7.19 (m, 1H) 8.3 (d, 2H) 12.1 (s, 1H) 12.3 (s, 1H). LC-MS calcd. for C13H9F3N3O [(M+H)+] 280, obsd. 279.9.
  • 32
  • [ 867366-91-4 ]
  • [ 214360-65-3 ]
  • [ 1590397-94-6 ]
YieldReaction ConditionsOperation in experiment
69% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 14.0h;Inert atmosphere; Sealed tube; Example 43 2-[(4-Fluoro-benzenesulfonyl)-methyl-amino]-N-(5-methoxy-4'-trifluoromethyl-biphenyl-3- ylmethyl)-acetamide A solution of 4,4,5,5-tetramethyl-2-(4-trifluoromethyl-phenyl)-[l,3,2]dioxaborolane(1.00 g, 3.68 mmol), <strong>[867366-91-4]3-bromo-5-methoxy-benzonitrile</strong> (0.78 g, 3.68 mmol) and potassium carbonate (0.51 g, 3.68 mmol) in DMF (5 mL) at 25C was purged with nitrogen gas and evacuated three times. The solution was then treated with teira 3s(triphenylphosphine)palladium(0) (212 mg, 184 muiotaetaomicron) and then sealed and heated to 120C for 14 h. The reaction mixture was cooled to 25 C, unsealed and poured into water. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave a brown solid. Flash chromatography (80/20 hexanes/ethyl acetate) afforded 5-methoxy- 4'-trifluoromethyl-biphenyl-3-carbonitrile (0.70 g, 69%) as a white solid.
  • 33
  • [ 117572-79-9 ]
  • [ 214360-65-3 ]
  • [ 1268096-99-6 ]
YieldReaction ConditionsOperation in experiment
79% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 14h;Inert atmosphere; Sealed tube; Example 46 2-[Ethyl-(4-fluoro-benzenesulfonyl)-amino]-N-(6-methoxy-4'-trifluoromethyl-biphenyl-3- ylmethyl)-acetamide A solution of 4,4,5,5-tetramethyl-2-(4-trifluoromethyl-phenyl)-[l,3,2]dioxaborolane(1.00 g, 3.68 mmol), <strong>[117572-79-9]3-bromo-4-methoxy-benzonitrile</strong> (0.78 g, 3.68 mmol) and potassium carbonate (0.51 g, 3.68 mmol) in DMF (5 mL) at 25C was purged with nitrogen gas and evacuated three times. The solution was then treated with teira 3s(triphenylphosphine)palladium(0) (212 mg, 184 muiotaetaomicron) and then sealed and heated to 120C for 14 h. The reaction mixture was cooled to 25 C, unsealed and poured into water. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave a brown solid. Flash chromatography (80/20 hexanes/ethyl acetate) afforded 6-methoxy- 4'-trifluoromethyl-biphenyl-3-carbonitrile (0.80 g, 79%) as a white solid.
  • 34
  • [ 35590-37-5 ]
  • [ 214360-65-3 ]
  • [ 1261600-44-5 ]
YieldReaction ConditionsOperation in experiment
71% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In N,N-dimethyl-formamide at 120℃; for 14h; Inert atmosphere; Sealed tube; 57 Example 57 Example 57 2-[(4-Fluoro-benzenesulfonyl)-isopropyl-amino]-N-[5-(4-trifluoromethyl-phenyl)-pyridin-3- ylmethyl] - acetamide A solution of 4,4,5,5-tetramethyl-2-(4-trifluoromethyl-phenyl)-[l,3,2]dioxaborolane(743 mg, 2.73 mmol), 5-bromo-nicotinonitrile (500 mg, 2.73 mmol) and potassium carbonate (358 mg, 2.73 mmol) in DMF (5 mL) at 25°C was purged with nitrogen gas and evacuated three times. The solution was then treated with teira/3's(triphenylphosphine)palladium(0) (158 mg, 137 μιηο) and then sealed and heated to 120°C for 14 h. The reaction mixture was cooled to 25°C, unsealed and poured into water. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave a brown solid. Flash chromatography (80/20 hexanes/ethyl acetate) afforded 5-(4- trifluoromethyl-phenyl)-nicotinonitrile (0.48 g, 71%) as a white solid. MH+ = 248.9.
  • 35
  • [ 179898-34-1 ]
  • [ 214360-65-3 ]
  • [ 1261859-03-3 ]
YieldReaction ConditionsOperation in experiment
84% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 14h;Inert atmosphere; Sealed tube; Example 11 2-[(4-Fluoro-benzenesulfonyl)-methyl-amino]-N-(5-fluoro-4'-trifluoromethyl-biphenyl-3- ylmethyl)-acetamide A solution of 4,4,5,5-tetramethyl-2-(4-trifluoromethyl-phenyl)-[l,3,2]dioxaborolane(1.00 g, 3.68 mmol), <strong>[179898-34-1]3-bromo-5-fluoro-benzonitrile</strong> (0.74 g, 3.68 mmol) and potassium carbonate (0.51 g, 3.68 mmol) in DMF (5 mL) at 25C was purged with nitrogen gas and evacuated three times. The solution was then treated with teira 3s(triphenylphosphine)palladium(0) (212 mg, 184 muiotaetaomicron) and then sealed and heated to 120C for 14 h. The reaction mixture was cooled to 25 C, unsealed and poured into water. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave a brown solid. Flash chromatography (80/20 hexanes/ethyl acetate) afforded 5-fluoro-4'- trifluoromethyl-biphenyl-3-carbonitrile (820 mg, 84%) as a white solid.
  • 36
  • [ 179897-89-3 ]
  • [ 214360-65-3 ]
  • [ 1261787-72-7 ]
YieldReaction ConditionsOperation in experiment
37% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In N,N-dimethyl-formamide at 120℃; for 14h; Inert atmosphere; Sealed tube; 12 Example 12 2- [(4-Fluoro-benzenesulfonyl)-methyl-amino]-N-(4-fluoro-4’ -trifluoromethyl-biphenyl-3-ylmethyl)-acetamide A solution of 4,4,5 ,5-tetramethyl-2-(4-trifluoromethyl-phenyl)- [1,3,2] dioxaborolane( 1.00 g, 3.68 mmol), 5-bromo-2-fluoro-benzonitrile (0.74 g, 3.68 mmol) and potassium carbonate (0.51 g, 3.68 mmol) in DMF (5 mL) at 25°C was purged with nitrogen gas and evacuated three times. The solution was then treated with tetrakis(triphenylphosphine)palladium(0) (212 mg, 184 tmol) and then sealed and heated to 120°C for 14 h. The reaction mixture was cooled to 25°C, unsealed and poured into water. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave a brown solid. Flash chromatography (80/20 hexanes/ethyl acetate) afforded 4-fluoro-4’- trifluoromethyl-biphenyl-3-carbonitrile (360 mg, 37%) as a white solid.
  • 37
  • [ 76-09-5 ]
  • 4-trifluoromethylphenyl-N,N-diisopropylaminoborane [ No CAS ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
256 mg Stage #1: 4-trifluoromethylphenyl-N,N-diisopropylaminoborane With methanol In ethyl acetate at -5 - 20℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: 2,3-dimethyl-2,3-butane diol In diethyl ether at 20℃; for 4h; Inert atmosphere; Schlenk technique;
Stage #1: 4-trifluoromethylphenyl-N,N-diisopropylaminoborane With methanol In toluene at -5 - 20℃; for 1h; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol In diethyl ether at 20℃; for 4h; 4.4. General procedure for the synthesis of pinacol arylboronates General procedure: In a reaction flask charged with CTA-NTf2 (100 mg) under argon atmosphere were added, in this following order: anhydrous toluene (4 mL), distilled iPr2NH (0.42 mL, 3 mmol), arylbromide (1 mmol),and amine-borane complex (0.3 mL, 2 mmol). The reaction mixture was then heated at 110 °C for 16 h. After total consumption of either starting material, the reaction mixture was cooled at -5 °C,quenched with anhydrous MeOH (2 mL), and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) and Et2O (2 mL), and the mixture was stirred for 4 h at room temperature. Then the reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution of HCl (0.1 N, 210 mL), followed by an aqueous solution of CuCl2 (50 g/L, 310 mL), dried over Na2SO4, filtered, and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et2O. The resulting filtrate was concentrated under vacuum and eventually purified by flash chromatography if some impurities were present in the residue.
256 mg Stage #1: 4-trifluoromethylphenyl-N,N-diisopropylaminoborane With methanol at -5 - 20℃; for 1h; Stage #2: 2,3-dimethyl-2,3-butane diol In diethyl ether at 20℃; for 4h; 89 Example 89: Preparation of 4,4,5,5-tetramethyl-2-(4-(trifiuoromethyl)phenyl)-l,3,2- dioxaborolane In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), l-chloro-4- (trifluoromethyl)benzene (0.13 mL, 1 mmol) and diisopropylammoborane (0.3 mL, 2 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et20 (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et20 (10 mL), and the organic phase was washed first with a solution of HC1 (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et20. The resulting filtrate was concentrated under vacuum to afford 4,4,5,5- tetramethyl-2-(4-(trifluoromethyl)phenyl)-l,3,2-dioxaborolane (256 mg, 94%). 1H NMR (300 MHz, CDCls) δ 7.92 (d, 2H, J= 8.0 Hz), 7,62 (d, 2H, J= 8.0 Hz), 1,36 (s, 12H); 13C NMR (100 MHz, CDC13) δ 135.16, 133.19, 132.77, 129.71, 126.10, 124.53, 124.48, 124.43, 124.38, 122.50, 84.42, 25.00; nB NMR (96 MHz, CDC13) δ +31.19; 19F NMR (376,5 MHz, CDCI3) δ -64.07; MS (EI) tR= 6.984 min; m/z: 272 (M+, 100%).
  • 38
  • [ 1401094-66-3 ]
  • [ 214360-65-3 ]
  • [ 1533422-41-1 ]
YieldReaction ConditionsOperation in experiment
71% With Pd(OTf)<SUB>2</SUB>(CH<SUB>3</SUB>CN)<SUB>4</SUB>; sodium hydrogencarbonate; N-acetyl-D-tert-leucine; silver carbonate; p-benzoquinone In tert-Amyl alcohol; water; dimethyl sulfoxide at 100℃; for 18h; Inert atmosphere; Schlenk technique; regioselective reaction; Methods General procedure: In a 50 ml Schlenk tube, starting material 1 (49.8 mg, 0.2 mmol), 4-methoxycarbonylphenylboronic acid pinacol ester (2) (104.8 mg, 0.4 mmol),Pd(OTf)2(MeCN)4 (11.4 mg, 0.02 mmol), Ac-D-tLeu-OH (3) (6.9 mg, 0.04 mmol),NaHCO3 (100.8 mg, 1.2 mmol), Ag2CO3 (110.3 mg, 0.4 mmol) and 1,4-benzoquinone (10.8 mg, 0.1 mmol) were combined. The flask was evacuated and backfilled with N2 three times, before a solution of dimethylsulfoxide (DMSO,6.0 mg, 0.076 mmol), water (20 mg, 1.1 mmol) and t-amyl-OH (1 ml, 0.2 M) was added. The reaction mixture was then stirred at 100 8C for 18 hours. After being allowed to cool to room temperature, the mixture was diluted with a 1:1 mixture of hexanes:ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated in vacuo, and the resulting residue purified by column chromatography using an eluent of hexanes:ethyl acetate. The product, 1b, was obtained as a light-yellow liquid (62.9 mg, 82%).The above procedure to prepare 1b is generally representative for all the products shown in Tables 3 and 4. Any deviations from this protocol are specified in the footnotes of the tables.
  • 39
  • [ 1608482-74-1 ]
  • [ 214360-65-3 ]
  • [ 1608482-92-3 ]
YieldReaction ConditionsOperation in experiment
62% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate In tetrahydrofuran; water at 60℃; for 16h; Sealed tube; Inert atmosphere; Preparation of2-( 4-chlor -6- ( 4-(trifluoromethyl)phenyl)pyridin-2-yl) thiazole: To a 2 dram vial equipped with a stir bar was added 2-(4,6-dichloropyridin-2- yl)thiazole (50 mg, 0.22 mmol), 4,4,5, 5-tetramethyl-2-(4-(trifluoromethyl)phenyl)- 1,3,2-dioxaborolane (59 mg, 0.22 mmol), Pd(dppf)Cl2 (8 mg, 11 μιηο) and K3PO4 (344 mg, 1.62 mmol). The vial was capped with a septum screwcap and then placed under N2 atmosphere. To the vial was added THF (1 mL) and water (0.5 mL). The mixture was placed in a 60 °C heating block with stirring for 16h. The reaction mixture was cooled to room temperatured; diluted with MeOH and then concentrated in vacuo. The resulting residue was dissolved/suspended in CH2C12 and then filtered through Celite. The filtrate was concentrated to afford a solid orange residue. This material was subjected to silica gel chromatography (hexanes:EtOAc, 100:0 to 95 :5) to afford 2-(4-chloro-6-(4-(trifluoromethyl)phenyl)pyridin-2-yl)thiazole as a white solid (46 mg, 62%). 1H-NMR (400MHz, CDC13) 8.23 (d, J=1.8 Hz, 2H), 8.21 (s, IH), 7.98 (d, J=3.3 Hz, IH), 7.80 (d, J=1.5 Hz, 2H), 7.78 (s, IH), 7.53 (d, J=3.3 Hz, IH).
  • 40
  • [ 14660-45-8 ]
  • [ 214360-65-3 ]
  • [ 455-24-3 ]
YieldReaction ConditionsOperation in experiment
80% With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I) In tetrahydrofuran at 70℃; for 16h; Inert atmosphere; Sealed tube; Carboxylation of Arylboronic Esters with PMC; Typical Procedure General procedure: In a glovebox, Cu(IPr)Cl catalyst and PMC (62.8 mg, 0.55 mmol,1.1 equiv) were charged to a glass reaction tube. A solution of 3(0.50 mmol) in THF (1.5 mL) was added, the tube was sealed, taken out of the glovebox, and heated at 70 °C for 16 h. After cooling tor.t., H2O (2 mL) was added and the reaction mixture was acidified with aqueous HCl (1 M), and saturated with sodium chloride. After extraction with EtOAc (3 × 5 mL), the organic phase was dried overanhydrous sodium sulfate and concentrated under vacuo. The product was purified by silica gel column chromatography.
  • 41
  • [ 873066-23-0 ]
  • [ 76-09-5 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
270 mg In diethyl ether at 20℃; for 4h;
256 mg In diethyl ether at 20℃; for 4h; 89 Preparation of 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 1-chloro-4-(trifluoromethyl)benzene (0.13 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et2O (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution of HCl (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2SO4 filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et2O. The resulting filtrate was concentrated under vacuum to afford 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (256 mg, 94%). 1H NMR (300 MHz, CDCl3) δ 7.92 (d, 2H, J = 8.0 Hz), 7,62 (d, 2H, J = 8.0 Hz), 1,36 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 135.16, 133.19, 132.77, 129.71, 126.10, 124.53, 124.48, 124.43, 124.38, 122.50, 84.42, 25.00; 11B NMR (96 MHz, CDCl3) δ +31.19; 19F NMR (376,5 MHz, CDCl3) δ -64.07; MS (EI) tR = 6.984 min; m/z: 272 (M+, 100%).
  • 42
  • [ 186828-50-2 ]
  • [ 214360-65-3 ]
  • [ 1616729-57-7 ]
YieldReaction ConditionsOperation in experiment
74% With palladium diacetate; potassium carbonate; di(1-adamantyl)-N-butylphosphine hydroiodide In 1,4-dioxane at 70℃; for 7h; Schlenk technique;
  • 43
  • [ 476004-80-5 ]
  • 2-(bis(4-methoxyphenyl)methyl)-5-methylthiophene [ No CAS ]
  • [ 214360-65-3 ]
  • 45
  • [ 24424-99-5 ]
  • [ 214360-65-3 ]
  • [ 196934-20-0 ]
YieldReaction ConditionsOperation in experiment
81% With 1,4-diaza-bicyclo[2.2.2]octane In 1,4-dioxane at 80℃; for 12h; Inert atmosphere; Green chemistry;
  • 46
  • [ 455-18-5 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
100% With 1,4-diaza-bicyclo[2.2.2]octane; Rh(Bpin){κ3-P,O,P-[9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene] In toluene at 100℃; for 15h; Inert atmosphere; Glovebox;
  • 47
  • [ 49669-13-8 ]
  • [ 214360-65-3 ]
  • 1-[6-(4-(trifluoromethyl)phenyl)pyridin-2-yl]ethanone [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In methanol; toluene for 24h; Reflux; 1-3 (1-3) Synthesis of 1-[6-(4-(trifluoromethyl)phenyl)pyridin-2-yl]ethanone (Compound L1-3) Compound L1-1 (900 mg, 4.5 mmol), Compound L1-2 (1.36 g, 5 mmol), 11 ml of a sodium carbonate solution (2N, 22.5 mmol), and tetrakis(triphenylphosphine)palladium [Pd(PPh3)4](260 mg, 0.22 mmol) were placed in a reaction flask, and then 27 ml of toluene and 3 ml of methanol were added to the reaction flask to obtain a mixture. The mixture was heated under reflux for 24 hours, and then the temperature of the mixture was slowly reduced to 20° C. The solvents in the mixture were drawn out of the reaction flask, and the residue in the reaction flask was washed several times with ethyl acetate and with a saturated sodium chloride solution to collect an organic layer, followed by dehydration of the organic layer using sodium sulfate (Na2SO4) to thereby obtain a crude product. The crude product was subjected to column chromatography (SiO2, ethyl acetate:n-hexane=1:6), followed by recrystallization in a mixed solvent having dichloromethane and n-hexane (dichloromethane:n-hexane=1:1) at 20° C., thereby obtaining white crystals (891 mg, 75% yield). (0052) The spectrum analysis for the white crystals is: 1H NMR (400 MHz, CDCl3): δ 8.02 (d, J=6.4, 2H), 7.95 (d, J=7.6 Hz, 1H), 7.937.91 (m, 2H), 7.75 (d, J=8.0, 2H), 2.81 (s, 3H); 19F NMR (376 MHz, CDCl3, 298K): δ -62.59 (s, 3F). The white crystals were confirmed to be Compound L1-3 having a chemical structure represented by
  • 48
  • [ 491-37-2 ]
  • [ 214360-65-3 ]
  • [ 128814-90-4 ]
YieldReaction ConditionsOperation in experiment
27% With palladium(II) trifluoroacetate; 5-Nitro-1,10-phenanthroline; oxygen In dimethyl sulfoxide at 100℃; for 48h;
27% With palladium(II) trifluoroacetate; 5-Nitro-1,10-phenanthroline; oxygen In dimethyl sulfoxide at 100℃;
  • 49
  • C11H15NO [ No CAS ]
  • [ 214360-65-3 ]
  • C18H18F3NO [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With palladium(II) trifluoroacetate; potassium tetrafluoroborate; silver carbonate; N-acetylglycine In tert-Amyl alcohol at 120℃; for 10h; Sealed tube;
  • 50
  • [ 1610703-69-9 ]
  • [ 214360-65-3 ]
  • 6-chloro-9-ethyl-8-(4-(trifluoromethyl)phenyl)-9H-purine [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate In 1,4-dioxane; water at 80℃; for 4h; Inert atmosphere; Sealed tube; 11 Example 11: Preparation of Intermediate M Example 11: Preparation of Intermediate MA vial was charged with 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-l,3,2-dioxaborolane (212 mg, 0.778 mmol), 6-chloro-9-ethyl-8-iodo-9H-purine (Intermediate D) (200 mg, 0.648 mmol), PdCl2(dppf) (23.72 mg, 0.032 mmol), dioxane (5 ml) and Na2C03 (0.7 ml, 1.400 mmol, 2M aquoues solution). The vial was sealed and the mixture was evacuated and backfilled with nitrogen (x 3), after which it was heated at 80°C for 4 h. The solution was then cooled and the solvent was removed in vacuo to afford a residue which was purified via column chromatography (silica gel, eluting 0-30% EtOAc in Hexanes) to afford 6-chloro-9-ethyl-8-(4-(trifluoromethyl)phenyl)-9H-purine (Intermediate M). MS (EI) Calc'd for C14H11C1F3N4 [M+H]+, 327; found 327.
  • 51
  • [ 544412-87-5 ]
  • [ 214360-65-3 ]
  • 5-methoxy-N-(perfluorophenyl)-4′-(trifluoromethyl)biphenyl-2-carboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; potassium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; silver carbonate In acetonitrile at 80℃; for 3h; Schlenk technique; Sealed tube; Inert atmosphere;
  • 52
  • [ 1570134-48-3 ]
  • [ 214360-65-3 ]
  • N-(2-(4,5-dihydrooxazol-2-yl)phenyl)-4'-(trifluoromethyl)-[1,1'-biphenyl]-2-carboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% With potassium acetate; copper diacetate; sodium carbonate; silver(l) oxide In dimethyl sulfoxide at 70℃; for 12h; Schlenk technique; Inert atmosphere;
  • 53
  • [ 329-14-6 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
49% With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; lithium hexamethyldisilazane In tetrahydrofuran at 80℃; for 10h; Schlenk technique; Inert atmosphere;
  • 54
  • [ 76-09-5 ]
  • [ 98-08-8 ]
  • [ 22092-92-8 ]
  • [ 325142-82-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
General procedure: In a glovebox, [Ir(OMe)(cod)]2 (33.1 mg, 0.050 mmol, 0.10 equiv), ICy?HCl (26.2 mg, 0.10 mmol,0.20 equiv), NaOt-Bu (19.2 mg, 0.20 mmol, 0.40 equiv) and benzene (1.0 mL) were added to a10 mL-sample vial with a Teflon-sealed screwcap, and stirred for 5 min at room temperature. 1g(113.1 mg, 1.0 mmol, 2.0 equiv) was added, and then the cap was screwed on to seal the vial. Thevial was stirred at 110 C for 18 h. The reaction mixture was cooled to room temperature. Pinacol(236 mg, 2.0 mmol, 4.0 equiv) in THF (2.0 mL) was added and the reaction mixture was stirred for1.5 h at room temperature under N2. The crude mixture was filtered through a pad of Celite andeluted with EtOAc. The filtrate was concentrated in vacuo and sampled for analysis by 1H NMRspectroscopy using 1,2-dichloroethane as an internal standard. The residue was purified by flashcolumn chromatography over silica gel eluting with hexane/EtOAc. Product-containing fractionswere concentrated in vacuo to give a pure borylated product.
  • 55
  • 3-bromo-1-methyl-6-nitroquinolin-4(1H)-one [ No CAS ]
  • [ 214360-65-3 ]
  • 1-methyl-6-nitro-3-(4-(trifluoromethyl)phenyl)quinolin-4(1H)-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water at 100℃; for 16h; Inert atmosphere; Sealed tube; 3.3 third step: 1-methyl-6-nitro-3- (4- (trifluoromethyl) phenyl) quinolin -4 (1H) - one 3-Bromo-1-methyl-6-nitroquinoline -4 (1H) - one 3c (50mg, 0.177mmol), 4- (trifluoromethyl) benzene boronic acid pinacol ester (97mg, 0.35mmol using a known method "JournaloftheAmerican ChemicalSociety, 2013,135 (50), 18730-18733" preparation derived), tetrakistriphenylphosphine palladium (21mg, 0.0177mmol), sodium carbonate (38mg, 0.35mmol) was suspended in 6mL dioxane and water (V / V = 5: 1) mixed solvent, purged with argon protection, 100 sealed tube was stirred for 16 hours.The filtrate was concentrated under reduced pressure, the resulting thin layer chromatography with a developing solvent system A and the residue was purified to give the title product, 1-methyl-6-nitro-3- (4- (trifluoromethyl) phenyl) quinoline - 4 (1H) - one 3d (68mg, yellow solid), yield: 100%.
  • 56
  • [ 99768-12-4 ]
  • [ 214360-65-3 ]
  • [ 1128268-16-5 ]
  • 57
  • 4,5,6,7-tetrachloro-1,3-dioxoisoindolin-2-yl 4-(trifluoromethyl)benzoate [ No CAS ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
76% With pyridine; caesium carbonate In ethyl acetate at 35℃; for 30h; Inert atmosphere; Irradiation;
  • 58
  • [ 1441984-36-6 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
74% With isonicotinate tert-butyl ester at 110℃; for 15h; Schlenk technique; Inert atmosphere;
  • 59
  • (E)-1,2-diphenylbut-1-en-1-yl 4-methylbenzenesulfonate [ No CAS ]
  • [ 214360-65-3 ]
  • (E)-(1-(4-(trifluoromethyl)phenyl)but-1-ene-1,2-diyl)dibenzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% With potassium phosphate monohydrate; palladium diacetate; ruphos In water; toluene at 70℃; Inert atmosphere;
  • 60
  • [ 398126-90-4 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
25% With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II); lithium hexamethyldisilazane In tetrahydrofuran at 40℃; for 20h; Schlenk technique; Inert atmosphere; Double Borylation of Diaryl Sulfoxides 1 (Table 2); Typical Procedure General procedure: A Schlenk tube was charged with diphenyl sulfoxide (1a) (41 mg, 0.20mmol), SPhos Pd G2 (7.2 mg, 0.010 mmol), B 2 pin 2 (0.20 g, 0.80 mmol),and LiN(SiMe 3 ) 2 (0.20 g, 1.2 mmol). THF (0.80 mL) was added to thetube and the resulting mixture was stirred at 80 °C for 20 h. After thereaction was complete, saturated aqueous NH 4 Cl (2 mL) was addedand the resulting biphasic mixture was extracted with Et 2 O (5 × 5mL). The combined organic layer was dried over Na 2 SO 4 , passedthrough a pad of silica gel, and concentrated under reduced pressure.The residue was purified by preparative TLC (hexane/EtOAc = 10:1) toprovide (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (2a)(54 mg, 0.26 mmol, 66%) as a colorless oil. All the resonances in the 1 Hand 13 C NMR spectra were consistent with the reported data. 12a
  • 61
  • [ 143028-36-8 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
7% With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II); lithium hexamethyldisilazane In tetrahydrofuran at 80℃; for 20h; Schlenk technique; Inert atmosphere; Double Borylation of Diaryl Sulfoxides 1 (Table 2); Typical Procedure General procedure: A Schlenk tube was charged with diphenyl sulfoxide (1a) (41 mg, 0.20mmol), SPhos Pd G2 (7.2 mg, 0.010 mmol), B 2 pin 2 (0.20 g, 0.80 mmol),and LiN(SiMe 3 ) 2 (0.20 g, 1.2 mmol). THF (0.80 mL) was added to thetube and the resulting mixture was stirred at 80 °C for 20 h. After thereaction was complete, saturated aqueous NH 4 Cl (2 mL) was addedand the resulting biphasic mixture was extracted with Et 2 O (5 × 5mL). The combined organic layer was dried over Na 2 SO 4 , passedthrough a pad of silica gel, and concentrated under reduced pressure.The residue was purified by preparative TLC (hexane/EtOAc = 10:1) toprovide (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (2a)(54 mg, 0.26 mmol, 66%) as a colorless oil. All the resonances in the 1 Hand 13 C NMR spectra were consistent with the reported data. 12a
  • 62
  • [ 15862-19-8 ]
  • [ 214360-65-3 ]
  • 5-(4-(trifluoromethyl)phenyl)-2,2'-bipyridine [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; ethanol; water at 80℃; Inert atmosphere;
  • 63
  • [ 1328064-88-5 ]
  • [ 214360-65-3 ]
  • C27H23F3N2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With n-butyllithium; iron(III)-acetylacetonate; 1,2-dichloro-2-methylpropane; zinc diacetate; cis-1,2-bis-(diphenylphosphino)ethene In tetrahydrofuran at 70℃;
  • 64
  • 4-bromo-3,5-dinitro-1H-pyrazole [ No CAS ]
  • [ 214360-65-3 ]
  • 3,5-dinitro-4-(4-(trifluoromethyl)phenyl)-1H-pyrazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With potassium phosphate; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II) In 1,4-dioxane; water at 100℃; for 48h; Sealed tube;
  • 65
  • [ 51-17-2 ]
  • [ 214360-65-3 ]
  • 1-(4-(trifluoromethyl)phenyl)-1H-benzo[d]imidazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With copper(I) sulfide; N,N,N,N,-tetramethylethylenediamine In methanol at 20℃; for 72h; 6 4.2 General procedure for compounds 6a-o (Table3) General procedure: A 10mL round bottom flask was charged with a magnetic stirring bar, benzimidazole 1 (59mg, 0.5mmol), boronic acid 2 (1.0mmol), Cu2S (4mg, 0.025mmol), and MeOH (2mL), followed with the addition of TMEDA (0.075mL, 0.5mmol). The flask was sealed with a septum, through which was inserted 18-gauche needle. This setup allowed air to go into the reaction and avoid contamination of a mixture. The reaction mixture was stirred from 400 to 600rpm for appropriate time and extracted with EtOAc (2×15mL). Combined organic layers were washed with saturated aqueous solution of ethylenediaminetetraacetic acid disodium salt (15mL), and then dried over anhydrous Na2SO4. Volatiles were removed under reduced pressure and the residue was purified by column chromatography (silica gel, hexanes - EtOAc) to yield the title product, which was characterized by 1H NMR, 13C NMR, HRMS, and melting point (if solid).
  • 66
  • t-butyl benzyl(cyclohexanecarbonyl)carbamate [ No CAS ]
  • [ 214360-65-3 ]
  • [ 419543-02-5 ]
YieldReaction ConditionsOperation in experiment
56% With bis(1,5-cyclooctadiene)nickel (0); potassium phosphate; 1,3-dicyclohexyl-1H-benzo[d]imidazol-3-ium chloride In water; toluene at 120℃; for 24h;
  • 67
  • [ 214360-65-3 ]
  • [ 202823-67-4 ]
  • (5s,8s)-1,4-bis(4-(trifluoromethyl))diphenyl-5,6,7,8-tetrahydro-5,8-ethanophthalazine [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In tetrahydrofuran; water at 100℃; for 12h; Inert atmosphere; 3 Example 3 2.3 g (10 mmol) of 1,4-dichloro-5,6,7,8-tetrahydro-5,8-ethane pyridazine,5.4 g (20 mmol) of 4-(trifluoromethyl)phenylboronic acid pinacol ester and 1.4 g (10 mmol) of potassium carbonate were added to a 250 mL round bottom flask, 0.2 g (0.3 mmol) of PdCl2(dppf) was added, and then poured into 30 mL Tetrahydrofuran and 15 mL of water, N2 protection, refluxed at 100° C. for 12 h. After cooling, dry tetrahydrofuran, and extract with dichloromethane to obtain the lower organic phase, spin down and chromatograph on a silica gel column with the eluent of petroleum ether:ethyl acetate=1:1 to obtain 2.0 g.1,4-Di(p-trifluoromethylphenyl)-5,6,7,8-tetrahydro-5,8-ethane pyridazine, white solid, yield44%.
  • 68
  • [ 583-68-6 ]
  • [ 214360-65-3 ]
  • 5-methyl-4'-(trifluoromethyl)-[1,1'-biphenyl]-2-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% Stage #1: 2-bromo-p-toluidine; 4-trifluoromethylphenylboronic acid pinacol ester With potassium carbonate In 1,2-dimethoxyethane; water for 0.5h; Stage #2: With bis-triphenylphosphine-palladium(II) chloride In 1,2-dimethoxyethane; water at 80℃;
  • 69
  • [ 149806-06-4 ]
  • [ 214360-65-3 ]
  • [ 356058-14-5 ]
YieldReaction ConditionsOperation in experiment
52% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water at 110℃; for 4h; Inert atmosphere; 8.1 6-(4-(trifluoromethyl)phenyl)nicotinaldehyde 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane 8a (3.23 g, 11.88 mmol),6-bromonicotinaldehyde 8b (1.84 g, 9.90 mmol),Tetratriphenylphosphine Palladium (1.14g, 0.99mmol)And sodium carbonate (5.25g, 49.49mmol)Dissolved in a mixed solution of 62 mL ethylene glycol dimethyl ether and water (V/V=55/7),The reaction was carried out at 110° C. for 4 hours under argon protection. Add 200 mL of water to the reaction solution.Extract with ethyl acetate (100 mL×3). Combine the organic phases and dry over anhydrous sodium sulfate. Filter and concentrate under reduced pressure. The residue is purified by silica gel column chromatography (eluent: System A).6-(4-(trifluoromethyl)phenyl)nicotinaldehyde 8c (1.55 g, white solid) was obtained, yield: 52.0%.
  • 70
  • S-(trifluoromethyl)dimesitylsulfanium triflate [ No CAS ]
  • [ 68716-49-4 ]
  • [ 214360-65-3 ]
  • 71
  • [ 142688-28-6 ]
  • [ 214360-65-3 ]
  • C22H15BrF3NO2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water at 100℃; Microwave irradiation; General Procedure for synthesis of Compound 7 General procedure: To the solution of corresponding compound 6 (0.58 mmol) in dimethoxyethane (2.0 mL) in microwave reaction vessel, were added compound 5 (0.53 mmol), Pd(PPh3)4 (0.018 g, 0.016 mmol) and aqueous 2M Na2CO3 solution (1.3 mL, 2.6 mmol). The reaction mixture was heated to 100 °C by microwave irradiation with power of 100 W. After the completion of reaction was confirmed, solvent was removed in vaccuo. The residue was purified on flash column chromatography using n-hexane (Hex):EA (9:1) as an eluent to obtain compound 7.
  • 72
  • 9-(3,5-dibromophenyl)-9H-carbazole [ No CAS ]
  • [ 214360-65-3 ]
  • 9-{3,5-bis[(4-trifluoromethyl)phenyl]phenyl}-9H-carbazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
62.1% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene for 30h; Reflux; Inert atmosphere; 3 Example 3 preparation of 9- {3,5-bis[(4-trifluoromethyl)phenyl]phenyl} -9H-carbazole 9-(3,5-Dibromophenyl)-9H-carbazole 4.01 g (10 mmol), 4-trifluoromethylphenylboronic acid pinacol ester 5.98 g (22 mmol), Tetrakis(triphenylphosphine)palladium 2.32 g (2 mmol), anhydrous potassium carbonate 8.16 g (60 mmol), water 36 g (2 mol), ethanol 46 g (l mol) and toluene 184 g (2 mol) were added to the reaction flask, respectively, and stirred it evenly. The reflux reaction was carried out under nitrogen protection for 30 h. The reaction solution was cooled to room temperature, allowed to stand, and separated layers. The organic layer was sanded and subjected to silica gel (200-300 mesh) column chromatography eluting with purified petroleum ether to obtain white solid. Yield 62.1%.
  • 73
  • [ 881658-92-0 ]
  • [ 214360-65-3 ]
  • C16H11F3N2O [ No CAS ]
  • 74
  • 6,7-dibromo-2,3-di(furan-2-yl)quinoxaline [ No CAS ]
  • [ 214360-65-3 ]
  • 6-bromo-2,3-di(furan-2-yl)-7-(4-(trifluoromethyl)phenyl)quinoxaline [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate at 80℃; Inert atmosphere; 12 4.2.4. General procedures for the preparation of compounds 7a-n and 8a-e General procedure: Compound 3h (1.0 mmol) and its relative borates (1.0 mmol)were added to 5mL dioxane. Pd(OAc)2 (0.01 mmol), s-phos(0.02 mmol), K3PO4 (2.0 mmol) were added to the mixture, whichwere then heated to 80 °C in N2 atmosphere. After completion ofthe reaction, the mixture was cooled to room temperature andevaporated the solvent under reduced pressure. The affordingcrude products were purified by column chromatography to givecompounds 7a-n and 8a-e.
  • 75
  • [ 2404-35-5 ]
  • [ 214360-65-3 ]
  • [ 1627205-05-3 ]
YieldReaction ConditionsOperation in experiment
47% With 2,2-bis((S)-4-phenyl-4,5-dihydrooxazol-2-yl)acetonitrile; (2,2-bis((S)-4-phenyl-4,5-dihydrooxazol-2-yl)acetonitrile)FeCl; lithium ethylmethyl amide In benzene at 50℃; for 48.17h; Inert atmosphere; Sealed tube;
  • 76
  • [ 61676-62-8 ]
  • (4-(trifluoromethyl)phenyl)zinc pivalate [ No CAS ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
81% With copper(I) iodide-lithium chloride In tetrahydrofuran at 20℃; Schlenk technique; Inert atmosphere;
  • 77
  • 3-phenyl-1-(1-(pyrimidin-2-yl)-1H-indol-2-yl)propan-1-one [ No CAS ]
  • [ 214360-65-3 ]
  • [ 1608124-61-3 ]
YieldReaction ConditionsOperation in experiment
65% With methanol; silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper diacetate In 1,4-dioxane at 110℃; for 16h; Sealed tube; Schlenk technique; Inert atmosphere; regioselective reaction;
  • 78
  • [ 54655-08-2 ]
  • [ 214360-65-3 ]
  • [ 1160172-06-4 ]
YieldReaction ConditionsOperation in experiment
72% With palladium diacetate; copper(II) acetate monohydrate In ethanol at 74℃; for 12h; Inert atmosphere; Schlenk technique;
  • 79
  • [ 455-24-3 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
97% With palladium diacetate; 2,2-Dimethylpropanoic anhydride; triethylamine; 1,4-di(diphenylphosphino)-butane In 1,4-dioxane at 160℃; for 15h;
34% With biphenyl; naphthalene-1,4-dicarbonitrile In water monomer; acetonitrile at 30℃; for 6h; Inert atmosphere; UV-irradiation;
With copper(I) tetrakis(acetonitrile)tetrafluoroborate; lithium perchlorate; sodium flouride; N-fluorobis(benzenesulfon)imide In acetonitrile for 6h; Irradiation; Inert atmosphere; Sealed tube;
  • 80
  • [ 368-94-5 ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
70% With bis(1,5-cyclooctadiene)nickel(0); tricyclohexylphosphine In toluene at 115℃; Inert atmosphere; Sealed tube; chemoselective reaction;
56% With bis(1,5-cyclooctadiene)nickel(0); potassium fluoride; triphenylphosphine; sodium chloride In octane; toluene at 140℃; for 24h; Schlenk technique; Inert atmosphere;
  • 81
  • [ 214360-65-3 ]
  • 2-­bromo-­8-­methoxyquinoline [ No CAS ]
  • 8-methoxy-2-(4-(trifluoromethyl)phenyl)quinoline [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In ethanol; water; toluene at 80℃; for 24h; Inert atmosphere; 8-methoxy-2-(4-(trifluoromethyl)phenyl)quinoline.(4) Under Ar atmosphere, amixture of compound 3 (47.1 mg, 0.20 mM), 4, 5, 5-tetramethy-2-(4-(trifluoromethyl)phenyl)-1, 3, 2-dioxaborolane (60.0 mg, 0.22 mM), and CsCO3 (78.2mg, 0.24 mM) dissolving in toluene/ethanol/ water (5/1/2, v/v) 3.2 mL, Pd (PPh3)4(41.6 mg, 0.036 mM) was added. The mixture was stirred at 80 °C for 24 h. Thesolvent was removed by reduced pressure distillation. The residue was dissolvedin 10 mL ethy lacetate. The solution was washed with water, saturated brine ,driedover MgSO4, filtered and distilled under reduced pressure. Finally,the productwere purified by column chromatography. (ethy lacetate:petroleum ether, 1:20).Whilte solid; 81.4 yield; mp 102.4 - 103.2 °C. 1H NMR (300 MHz, CDCl3)δ 8.34 - 8.28 (m, 2H), 8.23 (dd, J = 8.6, 2.1 Hz, 1H), 7.90 (dd, J = 8.6, 2.0Hz, 1H), 7.81 - 7.74 (m, 2H), 7.54 - 7.39 (m, 2H), 7.11 (d, J = 7.5 Hz, 1H). 13CNMR (75 MHz, CDCl3) δ 155.66, 154.61, 143.07, 140.18, 137.09,131.14, 130.71, 128.58, 127.95 (2C), 127.12, 126.06, 125.69 (q, J = 3.8 Hz),122.46, 119.35 (d, J = 2.9 Hz), 108.35, 56.15. ESI-MS m/z 304.07 [M + H]+.HRESIMS m/z 304.0493 [M + H]+ (calcd for C17H12F3NO,304.0493).
  • 82
  • 5-[4-chloro-3-(trifluoromethyl)phenyl]-3,6-dihydro-2H-1,3,4-oxadiazin-2-one [ No CAS ]
  • [ 214360-65-3 ]
  • 5-[2,4'-bis(trifluoromethyl)biphenyl-4-yl]-3,6-dihydro-2H-1,3,4-oxadiazin-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
41.0 mg With chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II); potassium carbonate; XPhos In 1,4-dioxane; water at 80℃; for 2h; Inert atmosphere; 51 Example 51 5-[2,4'-Bis(trifluoromethyl)biphenyl-4-yl]-3,6-dihydro-2H-1,3,4-oxadiazin-2-one In a reaction vessel, 5-[4-chloro-3-(trifluoromethyl)phenyl]-3,6-dihydro-2H-1,3,4- oxadiazin-2-one (1 18 mg, 424 μιηοΙ, Intermediate 64), 4,4,5,5-tetramethyl-2-[4- (trifluoromethyl)phenyl]-1,3,2-dioxaborolane (173 mg, 635 μιηοΙ), potassium carbonate (1 17 mg, 847 μιηοΙ) and 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (12.1 mg, 25.4 μιηοΙ) were suspended in 1.9 mL 1,4-dioxane and 630 μΙ_ water. The mixture was degassed with nitrogen for 5 min. Then, chloro(2-dicyclohexylphosphino-2',4',6'- triisopropyl-1,1 '-biphenyl)[2-(2'-amino-1,1 '-biphenyl)]palladium(ll) (10.0 mg, 12.7 μιηοΙ) was added. Nitrogen was passed through the reaction mixture. It was stirred at 80 for 2 hours in a heating block. The mixture was diluted with water and extracted with ethyl acetate three times. The combined organic layers were dried using a water-resistant filter and the filtrate was concentrated under reduced pressure. The residue was dissolved in DMSO, filtered and purified by preparative HPLC, to give 41.0 mg (95 % purity, 24 % yield) of the title compound. LC-MS (Method 2): R, = 1.34 min; MS (ESIneg): m/z = 387 [M-H]- 1H-NMR (400 MHz, DMSO-d6) δ [ppm]: 2.074 (0.60), 2.518 (1.30), 2.522 (0.87), 5.485 (16.00), 7.558 (2.86), 7.573 (4.04), 7.578 (4.21), 7.592 (4.18), 7.840 (4.85), 7.861 (4.14), 8.040 (1.89), 8.044 (1.99), 8.064 (1.84), 8.139 (3.75), 8.142 (3.55), 1 1.272 (5.26).
  • 84
  • [ 214360-65-3 ]
  • 4,4,5,5-tetramethyl-2-[4-(trifluoromethyl)cyclohexyl]-1,3,2-dioxaborolane [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With Rh-CAAC; hydrogen In dichloromethane at 25℃; for 24h; Autoclave; Molecular sieve; diastereoselective reaction;
  • 85
  • [ 16096-33-6 ]
  • [ 214360-65-3 ]
  • 1-phenyl-2-[4-(trifluoromethyl)phenyl]-1,2-dihydrobenz[e]-1,2-azaborin [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% Stage #1: 1-phenyl-1H-indole With lithium In tetrahydrofuran at -30℃; for 3h; Schlenk technique; Inert atmosphere; Stage #2: 4-trifluoromethylphenylboronic acid pinacol ester In tetrahydrofuran at -30 - 25℃; for 1h; Schlenk technique; Inert atmosphere;
  • 86
  • C23H34N2O5 [ No CAS ]
  • [ 214360-65-3 ]
  • [ 725229-27-6 ]
YieldReaction ConditionsOperation in experiment
53% With bis(1,5-cyclooctadiene)nickel (0); potassium phosphate; 1,3-dicyclohexyl-1H-benzo[d]imidazol-3-ium chloride; water In 1,4-dioxane at 120℃; for 24h; Inert atmosphere; Sealed tube;
  • 87
  • dimethyl(4-(trifluoromethyl)phenyl)sulfonium trifluoromethanesulfonate [ No CAS ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
44% With pyridine In water; acetone at 20℃; for 12h; UV-irradiation; Inert atmosphere;
  • 88
  • [ 214360-65-3 ]
  • 4,4,5,5-tetramethyl-2-[4-(trifluoromethyl)cyclohexyl]-1,3,2-dioxaborolane [ No CAS ]
  • 4,4,5,5-tetramethyl-2-[4-(trifluoromethyl)cyclohexyl]-1,3,2-dioxaborolane [ No CAS ]
YieldReaction ConditionsOperation in experiment
78 % de With [Rh(cod)(CI)(CAACMe2)]; hydrogen In hexane at 40℃; for 24h; Molecular sieve; Overall yield = 97 percent; Overall yield = 135 mg; diastereoselective reaction;
78 % de With [Rh(cod)(CI)(CAACMe2)]; hydrogen In hexane at 40℃; for 24h; Molecular sieve; Overall yield = 97 percent; 10; 25 Example 1 General procedure: Add 131 mg (0.5 mmol) of tert-butyl (2- (trifluoromethyl) phenylamino) formate, 3 mg (0.005 mmol) to the reaction flask.Cyclic (alkyl) (amino) carbene complex catalyst of rhodium, 125mg 4 A 5mL hexane, 5MPa into hydrogen and stirred for 24 hours at 40 .After the reaction, the solution was filtered, washed with dichloromethane, and then subjected to silica gel column chromatography (eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 20: 1).(2- (trifluoromethyl) cyclohexylamino) carboxylic acid tert-butyl ester was obtained in a yield of 98%, d.r. = 91: 9.
42 % de With chloro(1,5-cyclooctadiene)rhodium(I) dimer; borane-ammonia complex In 2,2,2-trifluoroethanol at 20℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube; Overall yield = 43 percent;
  • 89
  • [ 98-56-6 ]
  • [ 25015-63-8 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
75 %Spectr. With 1,1'-bis-(diphenylphosphino)ferrocene; tetrabutylammomium bromide; Ni(COD)(DQ); triethylamine In 1,4-dioxane at 100℃; for 24h; Sealed tube; Inert atmosphere;
  • 90
  • (E)-1-(4-(trifluoromethyl)phenyl)butan-1-one O-perfluorobenzoyl oxime [ No CAS ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
66% With 2,6-di-tert-butyl-4-methyl-phenol; potassium carbonate; 2-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)pyridine; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; tris<3,5-bis(trifluoromethyl)phenyl>phosphane; palladium dichloride In 1,2-dichloro-ethane at 120℃; for 12h; Inert atmosphere; Sealed tube;
  • 91
  • N-(2-bromothiazol-4-yl)-2-octyldodecanamide [ No CAS ]
  • [ 214360-65-3 ]
  • 2-octyl-N-(2-(4-(trifluoromethyl)phenyl)thiazol-4-yl)dodecanamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
58.8% With tris-(dibenzylideneacetone)dipalladium(0); Aliquat 336; potassium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 90℃; Sealed tube; 3 preparation2-octyl-N-(2-(4-(trifluoromethyl)phenyl)thiazol-4-yl)dodecylamide Dissolve N-(2-bromothiazol-4-yl)-2-octyldodecanamide (0.91 g, 1.93 mmol) in a 100 mL sealed tube with N,N-dimethylformamide (10 mL) in,Join4,4,5,5-Tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane(1.05 g, 3.86 mmol),Palladium catalyst Pd2(dba)3 (36.0 mg, 0.04 mmol),Ligand triphenylphosphine (56.3 mg, 0.21 mmol), K2CO3 (1.15 g, 8.21 mmol),Two drops of trioctyl methyl ammonium chloride,The reaction is carried out at 90°C for one to two days,After the reaction,To return to room temperature,Quench the reaction with saturated NH4Cl,The organic phase is extracted with ethyl acetate,The organic phase was washed with saturated brine, dried with anhydrous MgSO4, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate=50:1) to obtain compound 36 (0.61 g) as a yellow liquid with a yield of 58.8%.
  • 92
  • 1-(4-(trifluoromethyl)benzoyl)piperidine-2,6-dione [ No CAS ]
  • [ 73183-34-3 ]
  • [ 214360-65-3 ]
YieldReaction ConditionsOperation in experiment
98% With Wilkinson's catalyst In toluene at 160℃; for 15h; Inert atmosphere;
  • 93
  • 2-benzyl-N-(2,6-difluorophenyl)acrylamide [ No CAS ]
  • [ 214360-65-3 ]
  • (Z)-2-benzyl-N-(2,6-difluorophenyl)-3-(4-(trifluoromethyl)phenyl)acrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With tris(acetonitrile)(η5-pentamethylcyclopentadienyl)rhodium(III) hexafluoroantimonate; N-acetylleucine; silver pivalate; potassium carbonate In acetonitrile at 60℃; for 4h; Schlenk technique; Sealed tube; Inert atmosphere; regioselective reaction;
  • 94
  • 1-benzyl-N-(2-(pyridin-2-yl)propan-2-yl)-1H-indole-2-carboxamide [ No CAS ]
  • [ 214360-65-3 ]
  • 1-benzyl-N-(2-(pyridin-2-yl)propan-2-yl)-3-(4-(trifluoromethyl)-phenyl)-1H-indole-2-carboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With copper diacetate; sodium acetate; silver(l) oxide In dimethyl sulfoxide at 70℃; for 10h; Inert atmosphere; Schlenk technique; regioselective reaction;
  • 95
  • [ 214360-65-3 ]
  • 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)cyclohexyl)-1,3,2-dioxaborolane [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With 2,3-dimethyl-2,3-butane diol; tetrahydroxydiboron; [Rh(OH)(cod)]2 In ethanol at 50℃; for 18h; Schlenk technique; Inert atmosphere; chemoselective reaction;
  • 96
  • tert-butyl (2R)-2-(6-chloropyridin-2-yl)-1,1-difluoro-6-azaspiro[2.5]octane-6-carboxylate [ No CAS ]
  • [ 214360-65-3 ]
  • C24H25F5N2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 90℃; for 0.5h; 5.A Step A: tert-Butyl (2R)-2-(6-chloropyridin-2-yl)-1,1-difluoro-6-azaspiro[2.5]octane-6- carboxylate (E5a) To a solution of tert-butyl (2R)-2-(6-chloropyridin-2-yl)-1,1-difluoro-6-azaspiro[2.5]octane-6- carboxylate (Intermediate 9, I9) (50 mg, 0.14 mmol) in 1,4-dioxane (3 mL) and water (1 mL) were added 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (56.9 mg, 0.209 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (10 mg, 0.014 mmol), and potassium carbonate (39 mg, 0.28 mmol) and the reaction mixture was warmed to 90 °C and allowed to stir for 30 min. The reaction mixture was cooled to ambient temperature and water (50 mL) was added. The resulting mixture was extracted with ethyl acetate (3 × 20 mL). The combined organic extracts were washed with a saturated aqueous solution of sodium chloride (20 mL), dried (sodium sulfate), filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel chromatography, eluting with a gradient of petroleum ether:ethyl acetate - 100:0:0 to 80:20 to afford compound E5a. MS: m/z = 469.0 [M+H].
  • 97
  • [ 127427-45-6 ]
  • [ 214360-65-3 ]
  • [ 347-80-8 ]
YieldReaction ConditionsOperation in experiment
84% With potassium fluoride; 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene; copper(ll) bromide; magnesium chloride Alternatively, the title compound was prepared starting with an appropriate 2-bromo-2,2-difluoroacetamide 1a (250 mg, 1.0 mmol, 1.0 equiv.), KF (116 mg, 2.0 mmol, 2.0 equiv.),MgCl2 (95 mg, 1.0 mmol, 1.0 equiv.), appropriate 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (354 mg, 1.3 mmol, 1.3 equiv.), the L1 (130 mg, 0.2 mmol,0.2 equiv.), CuBr2 (22.3 mg, 0.1 mmol, 0.1 equiv.), and hexafluoropropanol (0.12 mmol/mL).The purification of the dry crude performed by column chromatography on silica gel providesthe amide 5a (222 mg, 0.84 mmol, 84%). The gram scale synthesis was performed on10 mmol of the starting 2-bromo-2,2-diuoroacetamide 1a and the amide 5a was preparedin 73% yield (1.93 g, 7.3 mmol).
  • 98
  • [ 145167-88-0 ]
  • [ 214360-65-3 ]
  • (±)-2-[1-(4-trifluoromethylphenyl)-1-phenylethyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% Stage #1: N,N-diisopropyl carbamic acid (1-phenylethyl) ester With sec.-butyllithium In diethyl ether at -78℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: 4-trifluoromethylphenylboronic acid pinacol ester In diethyl ether at -78 - 20℃; for 3h; Schlenk technique; Inert atmosphere;
  • 99
  • 2-phenylbutan-2-yl pivalate [ No CAS ]
  • [ 214360-65-3 ]
  • (S)-1-(2-phenylbutan-2-yl)-4-(trifluoromethyl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
69% With nickel(II) acetate tetrahydrate; 1,2-bis(3,5-dimethoxyphenyl)ethylene; lithium tert-butoxide In cyclohexane; iso-butanol at 80℃; for 24h; Inert atmosphere; stereospecific reaction;
  • 100
  • [ 3389-54-6 ]
  • [ 214360-65-3 ]
  • 1-(phenyl(4-(trifluoromethyl)phenyl)methyl)pyrrolidine [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With samarium; tetrakis(triphenylphosphine) palladium(0); samarium diiodide In tetrahydrofuran at 80℃; Inert atmosphere; Glovebox;
  • 101
  • [ 1351445-39-0 ]
  • [ 214360-65-3 ]
  • 1-(4-(trifluoromethyl)phenyl)naphthalene [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With SIPr-PdCl<SUB>2</SUB>-Py; cesium fluoride In tetrahydrofuran at 80℃; for 8h; Schlenk technique; Inert atmosphere; 3.1.3. General procedure for the Suzuki reaction General procedure: THF (2.5 mL) was injected into the mixture of ammonium salts (1 mmol), boronic acid (0.5 mmol), SIPr-PdCl2-Py (0.05 mmol) and CsF (1 mmol) in a Schleck tube under N2 atmosphere. After stirring for 8 h at 80 °C, the mixture was concentrated via reduced pressure. Finally, the residue was purified by flash chromatography on silica gel with an eluent to afford the target compound.
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