[ CAS No. 325142-82-3 ] {[proInfo.proName]}

Name: 325142-82-3|4,4,5,5-Tetramethyl-2-(3-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane|98%
Brand: Ambeed
SKU: A114283
Price: 7.0 USD
Availability: InStock
Rating: 92 (32 reviews)

,{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]}

2D 3D

Structure of 325142-82-3 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 325142-82-3 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 325142-82-3 ]

SDS Specification

Alternatived Products of [ 325142-82-3 ]

Product Details of [ 325142-82-3 ]

CAS No. :	325142-82-3	MDL No. :	MFCD05863925
Formula :	C₁₃H₁₆BF₃O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	GJNOCGLTCQPYAC-UHFFFAOYSA-N
M.W :	272.07	Pubchem ID :	2760604
Synonyms :

Calculated chemistry of [ 325142-82-3 ]

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 Å²

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 :	2.95

Safety of [ 325142-82-3 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 325142-82-3 ]

* 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.

Upstream synthesis route of [ 325142-82-3 ]
Downstream synthetic route of [ 325142-82-3 ]

[ 325142-82-3 ] Synthesis Path-Upstream 1~1

1
[ 62-53-3 ]
[ 325142-82-3 ]
[ 101-23-5 ]

Reference： [1] Journal of Organic Chemistry, 2016, vol. 81, # 9, p. 3942 - 3950

[ 325142-82-3 ] Synthesis Path-Downstream 1~87

1
2-chloro-3,4-dimethoxy benzonitrile [ No CAS ]
[ 325142-82-3 ]
5,6-dimethoxy-3'-trifluoromethyl-2-cyano-biphenyl [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2005,vol. 127,p. 4685 - 4696

2
[ 401-81-0 ]
[ 25015-63-8 ]
[ 325142-82-3 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 261 - 263

3
[ 98-08-8 ]
4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ No CAS ]
[ 325142-82-3 ]
[ 214360-65-3 ]

Reference： [1]Bulletin of the Chemical Society of Japan,2006,vol. 79,p. 1980 - 1982

4
[ 98-15-7 ]
[ 73183-34-3 ]
[ 325142-82-3 ]

Reference： [1]Angewandte Chemie - International Edition,2007,vol. 46,p. 5359 - 5363
[2]Angewandte Chemie - International Edition,2018,vol. 57,p. 10999 - 11003
Angew. Chem.,2018,p. 11165 - 11169,5

5
[ 76-09-5 ]
[ 1423-26-3 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
47%	In toluene; at 20℃; for 2h;	The title compound (47%, oil) was prepared from 3-trifluoromethylphenylboronic acid and pinacol. 1H NMR (300 MHz, CDCl3): delta 1.35 (s, 12H), 7.48 (t, 1H), 7.70 (d, 1H), 7.97 (d, 1H), 8.06 (bs, 1H).

Reference： [1]Advanced Synthesis and Catalysis,2013,vol. 355,p. 3553 - 3557
[2]Patent: WO2003/105860,2003,A1 .Location in patent: Page 35
[3]Organic Letters,2018,vol. 20,p. 6573 - 6577

6
[ 77295-66-0 ]
[ 325142-82-3 ]
[ 1008756-40-8 ]

Reference： [1]Tetrahedron Letters,2008,vol. 49,p. 1000 - 1003

7
[ 98-08-8 ]
[ 73183-34-3 ]
[ 1073339-21-5 ]
[ 325142-82-3 ]
[ 214360-65-3 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 390 - 391

8
[ 98-08-8 ]
[ 25015-63-8 ]
[ 1073339-21-5 ]
[ 325142-82-3 ]

Reference： [1]Journal of the American Chemical Society,2000,vol. 122,p. 12868 - 12869
[2]Journal of the American Chemical Society,2000,vol. 122,p. 12868 - 12869

9
[ 1158649-25-2 ]
[ 325142-82-3 ]
[ 1158649-31-0 ]

Reference： [1]Tetrahedron Letters,2009,vol. 50,p. 2430 - 2433
[2]Bioorganic and Medicinal Chemistry,2010,vol. 18,p. 7931 - 7939

10
[ 98-08-8 ]
[ 73183-34-3 ]
[ 1197374-02-9 ]
[ 325142-82-3 ]
[ 214360-65-3 ]

Reference： [1]Tetrahedron Letters,2009,vol. 50,p. 6176 - 6179

11
[ 591-50-4 ]
[ 325142-82-3 ]
[ 366-04-1 ]

Reference： [1]Angewandte Chemie - International Edition,2010,vol. 49,p. 1846 - 1849

12
[ 98-16-8 ]
[ 73183-34-3 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tert.-butylnitrite; dibenzoyl peroxide; In acetonitrile; at 20℃; for 4h;	EXAMPLE 2 Synthesis of 4,4,5,5-tetramethyl-2-(3-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane B2pin2 (1.0 mmol, 254 mg), benzoyl peroxide (0.02 mmol, 5 mg), 3-F3CC6H4NH2 (1 mmol, 161 mg) and acetonitrile (3 mL) were added to a 25 mL tube-type reactor, followed by the addition of tert-butyl nitrite (1.5 mmol, 154 mg). The reaction was conducted at room temperature for 4 h. The solution'was concentrated after the reaction and the resultant was purified by column chromatography (eluted by petroleum ether:ethyl acetate=30:1, V:V) to give 4,4,5,5-tetramethyl-2-(3-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane having the following structure: This compound is colorless liquid and obtained in 70% yield. Its NMR data are as follows: 1NNMR (400 MHz, CDCl3) delta 8.09~8.06(m, 1H), 7.97 (d, 1H, J=7.4 Hz), 7.70 (d, 1H, J=7.9 Hz), 7.48 (t, 1H, J=7.7 Hz), 1.36(s, 12H); 13C NMR (100 MHz, CDCl3) delta 137.9, 131.4, 131.3, 131.3, 131.2, 130.2, 129.8, 129.8, 128.8, 128.0, 127.8, 127.7, 127.7, 127.7, 125.6, 122.9, 84.2, 24.8.
70%	With tert.-butylnitrite; dibenzoyl peroxide; In acetonitrile; at 20℃; for 4h;	B2pin2 (1.0 mmol, 254 mg), benzoyl peroxide (0.02 mmol, 5 mg), 3-F3CC6H4NH2 (1 mmol, 161 mg) and acetonitrile (3 mL) were added to a 25 mL tube-type reactor, followed by the addition of tert-butyl nitrite (1.5 mmol, 154 mg). The reaction was conducted at room temperature for 4 h. The solution was concentrated after the reaction and the resultant was purified by column chromatography (eluted by petroleum ether : ethyl acetate = 30:1, V:V) to give 4,4,5,5-tetramethyl-2-(3-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane having the following structure: This compound is colorless liquid and obtained in 70% yield. Its NMR data are as follows: 1H NMR (400MHz, CDCl3) delta 8.09~8.06(m, 1H), 7.97 (d, 1H, J=7.4Hz), 7.70 (d, 1H, J=7.9Hz), 7.48 (t, 1H, J=7.7Hz), 1.36(s, 12H); 13C NMR (100MHz, CDCl3) delta 137.9, 131.4, 131.3, 131.3, 131.2, 130.2, 129.8, 129.8, 128.8, 128.0, 127.8, 127.7, 127.7, 127.7, 125.6, 122.9, 84.2, 24.8.

Reference： [1]Angewandte Chemie - International Edition,2010,vol. 49,p. 1846 - 1849
[2]Angewandte Chemie - International Edition,2010,vol. 49,p. 1846 - 1849
[3]Patent: US2012/184768,2012,A1 .Location in patent: Page/Page column 2
[4]Patent: EP2481742,2012,A1 .Location in patent: Page/Page column 4

13
[ 33252-29-8 ]
[ 325142-82-3 ]
[ 833457-45-7 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2010,vol. 20,p. 4507 - 4510

14
C₁₃H₁₄BrN₅O [ No CAS ]
[ 325142-82-3 ]
[ 701243-97-2 ]

Reference： [1]ACS Medicinal Chemistry Letters,2011,vol. 2,p. 34 - 38

15
[ 626-05-1 ]
[ 325142-82-3 ]
[ 180606-07-9 ]

Reference： [1]Organometallics,2019,vol. 38,p. 2963 - 2971

Yield	Reaction Conditions	Operation in experiment
59%	With sodium t-butanolate; In tetrahydrofuran; toluene; at 50℃; for 6h;Sealed tube;	General procedure: 1-Chloro-4-iodobenzene (48 mg, 0.20 mmol), 48 mg, 0.20 mmol)1,1-Dibornathethane (2, 107 mg, 0.30 mmol) and sodium tert-butoxide base (38 mg, 0.40 mmol) were placed in a 4 mL vial. Toluene / tetrahydrofuran (2.0 mL, 1: 1 mixed solution) was then added.The vial was reacted for six hours at 80 C sealed with a PTFE / silicone coated cap.The reaction solution was filtered through celite with dichloromethane, and the organic material was concentrated under reduced pressure. The products were then separated and purified on silica gel column chromatography Phi 2.0 cm × 8 cm under the specified eluent conditions under n-hexane: diethyl ether, 10: 1 eluent. As a result 2- (4-Chlorophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane boronated compound was produced. (32 mg, 67% yield); The procedure of Example 3 was followed except that aryl iodide was changed according to the following reaction formula (3), and the results are shown in Table 2.
171 mg	In diethyl ether; at 20℃; for 4h;	General procedure: To a solution of aniline (1 mmol) in 3 ml of distillated acetonitrile, at 0C, is added boron trifluoride etherate (1.5mmol 0.4 ml) and the solution is stirred for 5 minutes. Isoamyl nitrite (1.2 mmol, 0.2 ml) is then slowly added and thesolution is stirred for 15 minutes. Diisopropylamino borane (4 mmol, 0.6 ml) is then slowly added and the mixture isallowed to be stirred at room temperature for 3 hours. The reaction is then quenched, at 0C, by the slow addition of 2ml of distillated methanol and stirred 1 hour at room temperature. The mixture is concentrated under vacuum and asolution of pinacol (1.3 mmol, 153 mg) in 2 ml of diethyl ether is added and the mixture is stirred 4 hours at roomtemperature. 10 ml of diethyl ether is then added and the crude is washed three time with 6 ml of a aqueous solution of copper chloride (50 g/L). The organic phase is then filtered and died over Na2SO4 and concentrated under vacuum toafford pure aryl boronate. 113 mg of 2-(4-methoxy-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were obtained following the generalprocedure B using 123 mg of 4-methoxyaniline as a pale yellow oil, yield: 52.5%. 1H NMR (300 MHz, CDCl3) delta 7.75 (d, J= 8.7 Hz, 2H) 6.90 (d, J= 8.7 Hz, 2H) 3.83 (s, 3H) 1.33 (s, 12H). 11B NMR (100 MHz, CDCl3) delta 31.0513C NMR (75 MHz, CDCl3) deltaMS (EI) tR= 9.05 min; m/z: 234 (M+., 100%). 171 mg of 2-(3-trifluoromethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were obtained following the generalprocedure D according to example 3, using 260 mg of 3-trifluoromethylbenzenediazonium tetrafluoroborate as apale yellow oil.1H NMR (300 MHz, CDCl3) delta 7.97 (d, J = 7.4 Hz, 1H) 7.70 (d, J = 7.9 Hz, 1H) 7.48 (t, J = 7.6 Hz, 1H) 1.36 (s, 12H)11B NMR (100 MHz, CDCl3) delta 30.4813C NMR (75 MHz, CDCl3) delta 138.12; 128.16; 127.94; 118.30; 84.43; 25.02MS (EI) tR= 7.02 min; m/z: 272 (M+, 100%)

17
[ 77-85-0 ]
[ 325142-82-3 ]
Na(3-(CF₃)C₆H₄B(OCH₂)3CCH₃) [ No CAS ]

Reference： [1]Chemistry Letters,2011,vol. 40,p. 702 - 704

18
[ 77-85-0 ]
[ 1310-73-2 ]
[ 325142-82-3 ]
Na(3-(CF₃)C₆H₄B(OCH₂)3CCH₃) [ No CAS ]

Reference： [1]Chemistry Letters,2011,vol. 40,p. 702 - 704

19
2-bromo-1-iodo-3-methylbenzene [ No CAS ]
[ 325142-82-3 ]
[ 1319196-89-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃;	A solution of 2-bromo-l-iodo-3-methylbenzene (200 mg, 0.67 mmol), 4,4,5,5- tetramethyl-2-(3-(trifluoromethyl)phenyl)-l,3,2-dioxaborolane (220 mg, 0.81 mmol), sodium carbonate (214 mg, 2.02 mmol) and tetrakis(triphenylphophine) palladium (38.9 mg, 0.034 mmol) in toluene (2.0 mL)/EtOH (1.2 mL)/Water (0.2 mL) was heated in an oil bath at 80 C overnight. The reaction was concentrated and the resultant residue purified by column chromatography (100% Hexanes) to yield 2-bromo-3-methyl-3'- (trifluoromethyl)biphenyl.

Reference： [1]Patent: WO2011/90911,2011,A1 .Location in patent: Page/Page column 55; 56

20
2-bromo-1-iodo-3-methylbenzene [ No CAS ]
[ 325142-82-3 ]
[ 1319194-46-1 ]

Reference： [1]Patent: WO2011/90911,2011,A1

21
[ 1338718-15-2 ]
[ 325142-82-3 ]
[ 1338718-79-8 ]

Yield	Reaction Conditions	Operation in experiment
66.8%	With potassium acetate; sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; acetonitrile; at 100℃; for 0.666667h;Microwave irradiation; Inert atmosphere;	Step 1: Preparation of [(R)-1-(4-[5-tert-butoxycarbonylamino-2-(3-trifluoromethyl-phenyl)-thiazole-4-carbonyl]-amino}-2-methyl-2H-pyrazol-3-yl)-perhydro-azepin-4-yl]-carbamic acid benzyl ester In a microwave vial was placed ((R)-1-{4-[(2-bromo-5-tert-butoxycarbonylamino-thiazole-4-carbonyl)-amino]-2-methyl-2H-pyrazol-3-yl}-perhydro-azepin-4-yl)-carbamic acid benzyl ester (100.0 mg, 0.154 mmol), 4,4,5,5-tetramethyl-2-(3-trifluoromethyl-phenyl)-1,3,2-dioxaborolane (209.7 mg, 0.77 mmol, 5.0 eq.), sodium carbonate (49.0 mg, 0.46 mmol, 3.0 eq.), potassium acetate (45.4 mg, 0.46 mmol, 3.0 eq.), [1,1'-bis(diphenylphosphino)ferrocene]-dichloropalladium(II), complexed with dichloromethane (1:1) (25.2 mg, 0.03, mmol, 0.20 eq), ACN (9.0 mL), and water (1.9 mL). The reaction mixture was degassed with N2 for 10 minutes and then subjected to microwave irradiation at 100 C. for 40 minutes. The reaction mixture was diluted with ethyl acetate (50 mL) and then filtered through a pad of Celite. The filtrate was washed with 50% brine/water, water and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude was purified via flash column chromatography eluted with 50 to 100% ethyl acetate/heptane to give 73.5 mg (66.8%) of desired product as an oil. MS (ESI) m/z: 714.4 [M+H]+.

Reference： [1]Patent: US2011/251176,2011,A1 .Location in patent: Page/Page column 135-136

22
[ 19063-55-9 ]
[ 325142-82-3 ]
[ 1337936-13-6 ]

Reference： [1]Journal of Medicinal Chemistry,2011,vol. 54,p. 7055 - 7065

23
[ 401-81-0 ]
[ 73183-34-3 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
81%	With pyridine; cesium fluoride; In dimethyl sulfoxide; at 105℃; for 2h;Inert atmosphere; Schlenk technique;	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.
59%Chromat.	With copper(II) ferrite; potassium tert-butylate; In N,N-dimethyl-formamide; at 20℃; for 12h;Green chemistry;	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.

Reference： [1]Synthesis,2017,vol. 49,p. 4759 - 4768
[2]Green Chemistry,2012,vol. 14,p. 661 - 667
[3]Catalysis Communications,2016,vol. 85,p. 61 - 65

24
[ 98-16-8 ]
[ 325142-82-3 ]

Reference： [1]Advanced Synthesis and Catalysis,2013,vol. 355,p. 1083 - 1088
[2]Tetrahedron Letters,2014,vol. 55,p. 1702 - 1705
[3]Beilstein Journal of Organic Chemistry,2015,vol. 11,p. 1494 - 1502
[4]Journal of Organic Chemistry,2018,vol. 83,p. 12831 - 12837

25
[ 76-09-5 ]
C₁₃H₁₉BF₃N [ No CAS ]
[ 325142-82-3 ]

Reference： [1]Advanced Synthesis and Catalysis,2013,vol. 355,p. 1083 - 1088

26
trifluoromethylsilver [ No CAS ]
[ 210907-84-9 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
54%		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 muL, 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.

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 10330 - 10333
[2]Synthesis,2014,vol. 46,p. 2143 - 2148

27
[ 122918-25-6 ]
[ 325142-82-3 ]
[ 833457-45-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 4h;Reflux; Inert atmosphere;	2-bromo-6-cyanopyridine (0.50 g, 2.7 mmol), the colorless oily liquid of the preparation 1 (0.89 g, 3.3 mmol) and Pd(PPh3)4 (158 mg, 0.14 mmol) were added into a 100 ml single neck bottle, followed by adding THF (30 ml) and a potassium carbonate solution (potassium carbonate (0.94 g) in deionized water (7 ml)) to obtain a mixture. The mixture was heated under reflux for 4 hours under a nitrogen gas atmosphere. After the reaction was finished, the mixture was cooled to room temperature, followed by solvent removal by virtue of reduced pressure distillation to obtain a distilled mixture. Then, the distilled mixture was added with dichloromethane and water for extraction. The dichloromethane layer was collected and added with magnesium sulfate to remove water. The dichloromethane layer was then filtrated and the filtrate was collected. Next, the filtrate was concentrated by means of reduced pressure distillation to obtain a yellow solid product. The yellow solid product was subjected to column chromatography, in which a mixture of ethyl acetate and hexane(ethyl acetate: hexane=1:4) was used as an eluent. An eluate was collected followed by removing the eluent using a rotary evaporator. A white solid product was obtained (608 mg, 2.4 mmol, 90% yield. The spectrum analysis for the white solid product is: 1H NMR (400 MHz, CDCl3, 298K). delta(ppm): 8.27 (s, 1H), 8.22 (d, JHH=8.0 Hz, 1H), 8.02?7.90 (m, 2H), 7.76 ?7.59 (m, 3H).

Reference： [1]Patent: US2013/18189,2013,A1 .Location in patent: Paragraph 0082; 0083

28
[ 401-78-5 ]
[ 61676-62-8 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
86%		1-bromo-3-(trifluoromethyl)benzene (5.00 g, 22 mmol) was placed in a 250 ml reaction flask, followed by injecting and evacuating nitrogen gas three times. Next, dehydrated tetrahydrofuran (THF, 100 ml) was added into the reaction flask, followed by slowly adding 9.8 ml n-butyllithium in hexane solution (2.5M, 24 mmol) at -78 C. and stirring at the same temperature for 30 minutes. Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.0 ml, 24 mmol) was added into the reaction flask to obtain a mixture, and the temperature of the mixture was raised to room temperature, followed by stirring at room temperature for 12 hours. Next, water was added to terminate the reaction followed by removing THF using a rotary evaporator. Then, dichloromethane and water were added into the mixture for extraction. The dichloromethane layer was collected and added with magnesium sulfate to remove water therein. After water was removed, the dichloromethane layer was filtrated and the filtrate was collected. Next, the dichloromethane layer was concentrated by means of reduced pressure distillation to obtain a colorless oily liquid (5.21 g, 19 mmol, 86% yield). The spectrum analysis for the colorless oily liquid is: 1H NMR (400 MHz, CDCl3, 298K), delta(ppm): 8.04 (s, 1H), 7.95 (d, JHH=7.6 Hz, 1H), 7.68 (d, JHH=7.6 Hz, 1H), 7.46 (t, JHH=7.6 Hz, 1H), 1.34 (s, 12H).

Reference： [1]Patent: US2013/18189,2013,A1 .Location in patent: Paragraph 0066; 0067

29
[ 325142-82-3 ]
C₁₆H₉F₆NO₂ [ No CAS ]

Reference： [1]Patent: US2013/18189,2013,A1

30
[ 325142-82-3 ]
2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)-6-(3-(trifluoromethyl)phenyl)pyridine [ No CAS ]

Reference： [1]Patent: US2013/18189,2013,A1

31
[ 325142-82-3 ]
C₁₃H₉F₃N₂O [ No CAS ]

Reference： [1]Patent: US2013/18189,2013,A1

32
[ 325142-82-3 ]
C₁₅H₈F₆N₄ [ No CAS ]

Reference： [1]Patent: US2013/18189,2013,A1

33
[ 49669-13-8 ]
[ 325142-82-3 ]
[ 1227055-11-9 ]

Yield	Reaction Conditions	Operation in experiment
67%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 16h;Reflux; Inert atmosphere;	The colorless oily liquid of Preparation 1 (0.68 g, 2.5 mmol), 6-acetyl-2-bromopyridine (0.50 g, 2.5 mmol) and tetrakis(triphenylphosphine)palladium(Pd(PPh3)4, 144 mg, 0.13 mmol) were added in a 100 ml single neck bottle followed by adding THF (25 ml) and a potassium carbonate solution (potassium carbonate (0.69 g) in deionized water (5 ml)) to obtain a mixture. The mixture was heated under reflux for 16 hours under a nitrogen gas atmosphere. After the reaction was finished, the mixture was cooled to room temperature, followed by removing solvent by virtue of reduced pressure distillation to obtain a distilled mixture. Then, the distilled mixture was added with dichloromethane and water for extraction. The dichloromethane layer was collected and added with magnesium sulfate to remove water. The dichloromethane layer was then filtrated and the filtrate was collected. Next, the filtrate was concentrated by means of reduced pressure distillation to obtain a yellow crude product. The resultant yellow crude product was subjected to column chromatography, in which a mixture of ethyl acetate and hexane(ethyl acetate: hexane=1:8) was used as an eluent. An eluate was collected followed by removing the eluent using a rotary evaporator. A white solid product was obtained (446 mg, 1.7 mmol, 67% yield). The spectrum analysis for the white solid product is: 1H NMR (400 MHz, CDCl3, 298K), delta(ppm): 8.34 (s, 1H), 8.27 (d, JHH=8.0 Hz, 1H), 8.02 (dd, JHH=6.8 Hz, 2.0 Hz, 1H), 7.98?7.90 (m, 2H), 7.70 (d, JHH=8.0 Hz, 1H), 7.63 (t, JHH=8.0 Hz, 1H), 2.82 (s, 3H).

Reference： [1]Patent: US2013/18189,2013,A1 .Location in patent: Paragraph 0070; 0071

34
N,N-bis(2-cyano-5-methoxyphenyl)-3-(o-tolyl)propanamide [ No CAS ]
[ 325142-82-3 ]
N,N-bis(2-cyano-5-methoxyphenyl)-3-(4-methyl-3'-(trifluoromethyl)[1,1'-biphenyl]-3-yl)propanamide [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 18056 - 18059

35
[ 106-38-7 ]
[ 325142-82-3 ]
[ 97067-19-1 ]

Reference： [1]Advanced Synthesis and Catalysis,2013,vol. 355,p. 3553 - 3557

36
[ 76-09-5 ]
[ 22092-92-8 ]
[ 454-87-5 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
61%		Example 3: General procedure D for the synthesis of the arylpinacolboronates by arylation of diisopropylaminoborane, catalysed by ferrocene (1%), followed by methanolysis and transesterification In a dried tube reactor under argon as described in example 2, the arenediazonium salt (1 mmol) and the ferrocene (IotaOmicronmuiotaetaomicronIota, 1.8mg) were dissolved in 2mL of anhydrous CH3CN. Diisopropylaminoborane (2mmol, 226mg) was then added to the solution and the mixture was stirred for 2h30 at room temperature. The reaction mixture was quenched by a slow addition of anhydrous MeOH at 0C (2mL) and stirred for an additional hour at room temperature. After removal of all the volatiles, 1.3eq of pinacol was added in Et20 (2mL), the mixture was stirred 4h at room temperature. The crude mixture was washed with a 50g/L CuCl2 solution (2 x 5mL). The organic layer were separated, dried over Na2S04, filtered and concentrated to dryness. The resulted oil was dissolved with CH2C12 and filtered of a pad of silica gel, eluting with CH2C12 to afford the corresponding boronate. Example 33: Synthesis of the arylpinacolboronates by arylation of diisopropylaminoborane., catalysed by a titanocene (1%), followed by methanolysis and transesterification Compounds VIAI to VIA22, IA24 and VIA26 were prepared using the procedure D (example 3), by replacing the ferrocene (1%) by the titanocene Cp2TiCl2 (1%). The yields are shown in the table 1.

Reference： [1]Patent: WO2014/9169,2014,A1 .Location in patent: Page/Page column 53-54; 67-68

37
C₁₃H₁₉BF₃N [ No CAS ]
[ 325142-82-3 ]

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 1702 - 1705

38
[ 76-09-5 ]
[ 1412429-43-6 ]
[ 325142-82-3 ]

Yield	Reaction Conditions	Operation in experiment
	In diethyl ether; at 20℃; for 4h;Inert atmosphere;	General procedure: In a dried tube reactor under argon, were dissolved the diazonium salt (1 mmol) and titanocenedichloride (10mumol, 2.5mg) in 2mL of anhydrous CH3CN. Diisopropylaminoborane (2mmol 226mg) is then added to the solution and stirred for 2h30 at room temperature. The reaction mixture is quenched by a slow addition of anhydrous MeOH at 0C (2mL) and stirred for an additional hour at room temperature. After removal of all the volatiles, 1.3eq of pinacol is added in Et2O (2mL), the mixture is stirred 4h at room temperature. The crude mixture is washed with a 50g/L CuCl2 solution (2 x 5mL). The organic layer is separated, dried over Na2SO4, filtred and concentrated to dryness. The resulted oil is dissolved with CH2Cl2 and filtered of a pad of silica gel, eluting with CH2Cl2 to afford the corresponding boronate.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 1702 - 1705

39
[ 1401094-66-3 ]
[ 325142-82-3 ]
[ 1533422-42-2 ]

Yield	Reaction Conditions	Operation in experiment
73%	With Pd(OTf)2(CH3CN)4; 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;	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.

Reference： [1]Nature Chemistry,2014,vol. 6,p. 146 - 150

40
2-isobutyl-2-(2-methoxy-5-((4a-methyl-2,3,4,4a-tetrahydro-1H-carbazol-9(9aH)-yl)sulfonyl)phenyl)-4-methylpentanenitrile [ No CAS ]
[ 325142-82-3 ]
2-(5-((7-(3-(trifluoromethyl)phenyl)-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazol-9(9aH)-yl)sulfonyl)-2-methoxyphenyl)-2-isobutyl-4-methylpentanenitrile [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 10807 - 10813

41
1-[(6-bromo-imidazo[1,2-a]pyridine-3-sulfonyl)]-6-{{1-[(methyl)]-4-pyrazolyl}-1H-pyrazolo[4,3-b]pyridine [ No CAS ]
[ 325142-82-3 ]
6-(1-methyl-1H-pyrazol-4-yl)-1-((6-(3-(trifluoromethyl)phenyl)imidazo[1,2-a]pyridin-3-yl)sulfonyl)-1H-pyrazolo[4,3-b]pyridine [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2015,vol. 58,p. 2513 - 2529

42
bis(3-(trifluoromethyl)phenyl)iodonium acetate [ No CAS ]
[ 73183-34-3 ]
[ 325142-82-3 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 14068 - 14071

43
bis(3-(trifluoromethyl)phenyl)iodonium bromide [ No CAS ]
[ 325142-82-3 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 14068 - 14071

44
[ 98-08-8 ]
[ 325142-82-3 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 14068 - 14071

45
4-(5-chloro-2-methoxyphenyl)-2-methylpyridine [ No CAS ]
[ 325142-82-3 ]
4-(4-methoxy-3'-(trifluoromethyl)-[1,1'-biphenyl]-3-yl)-2-methylpyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With palladium diacetate; potassium carbonate; XPhos; In tert-Amyl alcohol; water; at 100℃; for 18h;Inert atmosphere;	Preparation 58 4-(4-methoxy-3'-(trifluoromethyl)-[1,1'-biphenyl]-3-yl)-2-methylpyridine To a mixture of 4-(5-chloro-2-methoxyphenyl)-2-methylpyridine (Preparation 59, 55 g, 0.24 mol), 4,4,5,5-tetramethyl-2-(3-(trifluoromethyl)phenyl)-1 ,3,2-dioxaborolane (104.8 g, 0.35 mol) and potassium carbonate (97.4 g, 0.71 mmol) was added 2-methyl-2- butanol (660 mL) and water (385 mL). The reaction mixture was sparged with nitrogen and degassed in vacuo before the addition of palladium acetate (1.06 g, 470 mmol) and XPhos (4.48 g, 9.40 mmol). The reaction was heated to 100C for 18 hours, then cooled, diluted with EtOAc (200 mL) and filtered through Celite. The filtrate was separated, the organic layer collected and concentrated in vacuo. The residue was purified using silica gel column chromatography eluting with 5-100% EtOAc in heptanes. The residue was dissolved in EtOAc (250 mL) and extracted into 1 M HCI (aq) (2 x 500 mL). The aqueous layers were combined and basified by the addition of concentrated aqueous NaOH solution. The product was extracted into EtOAc (2 x 200 mL), the organic layers combined, dried over magnesium sulphate and concentrated in vacuo to afford the title compound (74.2 g, 81 %). (0906) 1 H NMR (400MHz, CDCI3): delta ppm 2.64 (s, 3H), 3.90 (s, 3H), 7.1 1 (d, 1 H), 7.34 (dd, 1 H), 7.37 (s, 1 H), 7.55 (d, 1 H), 7.61-7.55 (m, 2H), 7.62 (dd, 1 H), 7.76 (d, 1 H), 7.82 (s, 1 H), 8.59 (d, 1 H).

Reference： [1]Patent: WO2015/181797,2015,A1 .Location in patent: Page/Page column 118; 119

46
[ 325142-82-3 ]
(4-(4-methoxy-3'-(trifluoromethyl)-[1,1'-biphenyl]-3-yl)pyridin-2-yl)methanol [ No CAS ]