[ CAS No. 68716-49-4 ] {[proInfo.proName]}

Name: 68716-49-4|2-(4-Bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane|98%
Brand: Ambeed
SKU: A118429
Price: 5.0 USD
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2D 3D

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Quality Control of [ 68716-49-4 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 68716-49-4 ]

SDS Specification

Alternatived Products of [ 68716-49-4 ]

Product Details of [ 68716-49-4 ]

CAS No. :	68716-49-4	MDL No. :	MFCD11110553
Formula :	C₁₂H₁₆BBrO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	AZCNDGAXOZWQPV-UHFFFAOYSA-N
M.W :	282.97	Pubchem ID :	10755376
Synonyms :

Calculated chemistry of [ 68716-49-4 ]

Physicochemical Properties

Num. heavy atoms :	16
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.5
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	70.62
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) :	-5.47 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	3.6
Log Po/w (WLOGP) :	2.75
Log Po/w (MLOGP) :	2.42
Log Po/w (SILICOS-IT) :	2.51
Consensus Log Po/w :	2.26

Druglikeness

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

Water Solubility

Log S (ESOL) :	-4.07
Solubility :	0.0239 mg/ml ; 0.0000844 mol/l
Class :	Moderately soluble
Log S (Ali) :	-3.67
Solubility :	0.0599 mg/ml ; 0.000212 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-4.84
Solubility :	0.00404 mg/ml ; 0.0000143 mol/l
Class :	Moderately soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.88

Safety of [ 68716-49-4 ]

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

Application In Synthesis of [ 68716-49-4 ]

* 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 [ 68716-49-4 ]
Downstream synthetic route of [ 68716-49-4 ]

[ 68716-49-4 ] Synthesis Path-Upstream 1~6

1
[ 3842-55-5 ]
[ 68716-49-4 ]
[ 23449-08-3 ]

Yield	Reaction Conditions	Operation in experiment
66%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 70℃; for 5 h;	2.68 g (10 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine(2-chloro-4,6-diphenyl-[1,3,5]-triazine),2.82 g (10.0 mmol) of 4-bromo-phenylboronic acid pinacol ester(4-bromo-phenylboronic acid pinacol ester),0.58 g (0.5 mmol) of Pd(PPh3)4 and 4.14 g (30.0 mmol) ofK2CO3 was dissolved in 60 mL of a mixture of THF and H2O (2:1 by volume) to obtain a solution which was then stirred at 70C for about 5 hours.And then extracted three times with 60 mL of water and 60 mL of diethyl ether.The organic layer was collected and dried over magnesium sulfate to evaporate the solvent.The residue was separated and purified by silica gel column chromatography to obtain 2.56 of Intermediate I-7(yield: 66percent).

Reference： [1] Patent: TWI614236, 2018, B, . Location in patent: Paragraph 0122; 0123

2
[ 24388-23-6 ]
[ 68716-49-4 ]
[ 269410-06-2 ]
[ 594823-67-3 ]

Reference： [1] Organic Letters, 2010, vol. 12, # 23, p. 5474 - 5477

3
[ 108-86-1 ]
[ 76-09-5 ]
[ 1359224-18-2 ]
[ 68716-49-4 ]
[ 594823-67-3 ]

Reference： [1] Chemical Communications, 2015, vol. 51, # 14, p. 2878 - 2881

4
[ 108-86-1 ]
[ 76-09-5 ]
[ 1350843-22-9 ]
[ 68716-49-4 ]
[ 594823-67-3 ]

Reference： [1] Chemical Communications, 2015, vol. 51, # 14, p. 2878 - 2881

5
[ 108-86-1 ]
[ 76-09-5 ]
[ 2890-88-2 ]
[ 24388-23-6 ]
[ 68716-49-4 ]
[ 594823-67-3 ]

Reference： [1] Chemical Communications, 2015, vol. 51, # 14, p. 2878 - 2881

6
[ 1511-62-2 ]
[ 68716-49-4 ]
[ 1234319-14-2 ]

Reference： [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 38, p. 12543 - 12548[2] Angew. Chem., 2018, vol. 130, p. 12723 - 12728,6

[ 68716-49-4 ] Synthesis Path-Downstream 1~73

1
[ 673-40-5 ]
[ 73183-34-3 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
68%	With eosin y; In neat (no solvent, solid phase); for 1h;Milling; Irradiation;	General procedure: A mixture of 1 (0.369 mmol), 2 (0.369 or 0.554 mmol) and eosin Y (11.96 mg; 5 mol %)was mixed in a 25 mL PMMA milling jar with 15 ZrO2 balls of 5 mm in diameter at 25 Hz.Irradiation of the reaction mixture was achieved by wrapping the milling jar with a greenLED strip (90 cm; see picture in section 2). After the milling was stopped, the reactionmixture was recovered from the milling jar and the product was purified by columnchromatography (SiO2, eluent 100:1 n-pentane/ethyl acetate).

Reference： [1]Organic Letters,2003,vol. 5,p. 4635 - 4638
[2]Tetrahedron Letters,2000,vol. 41,p. 8683 - 8686
[3]Advanced Synthesis and Catalysis,2012,vol. 354,p. 2625 - 2628
[4]Beilstein Journal of Organic Chemistry,2014,vol. 10,p. 981 - 989
[5]Chemical Communications,2019,vol. 55,p. 6201 - 6204
[6]ChemSusChem,2020,vol. 13,p. 1715 - 1719
[7]ChemistryOpen,2017,vol. 6,p. 345 - 349
[8]Beilstein Journal of Organic Chemistry,2017,vol. 13,p. 1463 - 1469
[9]Science,2019,vol. 366,p. 1500 - 1504

2
[ 589-87-7 ]
[ 25015-63-8 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
		[00438] In a reaction tube under nitrogen, a mixture of PdCl2(dppf)CH2Cl2 (22 mg; 0.027 mmol) and triethylamine (0.36 ml; 2.58 mmol) in dioxane (4 ml; dried over 4 ? sieves) was sealed and stirred at 80 C. overnight (18 h). After cooling to room temperature, HB(pin) (0.19 ml; 1.31 mmol) and 1-bromo-4-iodobenzene (244 mg; 0.862 mmol) were added and the reaction mixture was stirred at room temperature. [00439] GC analysis after 66 h showed a peak at 8.63 mins which was identified by GC/MS as the desired compound.

Reference： [1]Journal of Organometallic Chemistry,2001,vol. 640,p. 197 - 199
[2]Journal of Organometallic Chemistry,2001,vol. 640,p. 197 - 199
[3]Organic Letters,2006,vol. 8,p. 261 - 263
[4]Chemical Communications,2002,p. 1566 - 1567
[5]Angewandte Chemie - International Edition,2002,vol. 41,p. 563 - 572
[6]Patent: US6680401,2004,B1 .Location in patent: Page column 70

3
[ 76-09-5 ]
[ 5467-74-3 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
99.7%	In acetonitrile; at 20℃; for 1.5h;	A suspension of commercially available 4-bromoplienyl boronic acid (18, 253.0 g, 1.24 mol) in acetonitrile (1000 ml) was stirred at room temperature. Pinacol (150.9g, 1.27 mol) was added and stirring was continued 1.5 h until a clear solution was obtained. The solvent was removed at 30-35C under vacuum to give crude 4- bromo-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)benzene (20, 349.9g, 99.7% yield) as light yellow solid. (1H NMR (300 MHz, CDCl3) delta 7.66 (d, J= 8.4 Hz, 2H), 7.50 (d, J= 8.4 Hz, 2Hz), 1.34 (s, 12H) ppm).
	In toluene;	In the scheme shown below is the description of a phosphonic acid containing compound. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (34A) to the corresponding pinacol ester 35A upon stirring with pinacol in toluene. Treatment of 35A with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produces the dimethylphosphonate derivative 36A in good yield. Suzuki coupling of 36A with 26A gives the expected biphenyl derivative that is deprotected by first hydrolysis in aqueous methanol and triethylamine, hydrogenolysis over palladium on carbon and finally treatment with bromotrimethylsilane to give the desired product 37A.
	In toluene;	[00247] In the scheme shown below is the description of a phosphonic acid containing compound. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (28) to the corresponding pinacol ester 29 upon stirring with pinacol in toluene. Treatment of 29 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produced the dimethylphosphonate derivative 30 in good yield.[00248] Suzuki coupling of 30 with 24 gives the biphenyl derivative 31. Catalytic hydrogenation of 31 over palladium on carbon removes the ben2yl protecting group and reduces the double bond to give ketone 32. Reduction of 32 with borane dimethylsulfide complex in the presence of a catalytic amount of tetrahydro-l-methyl-3,3-diphenyl-lH,3H- pyrrolo[l,2-c][l,3,2]oxazaborole, (R-CBS) followed by treatment with bromotrimethylsilane and an aqueous workup gives compound 33.; In the scheme shown below is the description of a phosphonic acid containing compound. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (28) to the corresponding pinacol ester 29 upon stirring with pinacol in toluene. Treatment of 29 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produced the dimethylphosphonate derivative 30 in good yield.

	In toluene;	In the scheme shown below, the synthesis of a phosphonic acid compound is described. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (18) to the corresponding pinacol ester 19 upon stirring with pinacol in toluene. Treatment of 19 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produces the dimethylphosphonate derivative 20 in good yield.[00267] Suzuki coupling of 20 with 9 gives the expected biphenyl derivative that is deprotected by hydrogenolysis over palladium on carbon and finally treatment with bromotrimethylsilane and aqueous HF treatment gives the desired product 21.
	In toluene;	2-Hydroxy-4-bromobenzaldehyde 4 was prepared by reaction of 3- bromophenol with paraformaldehyde in the presence of magnesium chloride and excess triethylamine in acetonitrile. Condensation of 4 with aniline (5) gave the desired imine 6a that was converted to the benzyl protected derivative 6b upon treatment with benzyl bromide and potassium carbonate in DMF. In the next step, 3b EPO <DP n="183"/>is treated with titanium tetrachloride and iV-ethyldiisopropylamine followed by treatment with 6b to effect enantiospecific condensation providing 7. Treatment of 7 with excess N,O-bistrimethylsilyl-acetamide followed by a catalytic amount of tetrabutylammonium fluoride hydrate results in ring closure to the desired beta-lactam (8) while maintaining the TBS protecting group on the benzylic alcohol. Commercially available 4-bromophenylboronic acid (9) is converted to the corresponding pinacol ester 10 by stirring with pinacol in toluene. Treatment of 10 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane in toluene produces the dimethylphosphonate derivative 11 (an adaptation of the published procedure; Jiao, X. Y.; Bentrude, W. G. J Org. Chern. 2003, 68, 3303-3306). Suzuki coupling of 8 with 11 gives the expected biphenyl derivative 13 that is deprotected by hydrogenolysis over palladium on carbon, treatment with bromotrimethylsilane, and treatment with aqueous HF to give the product 12.

Reference： [1]Patent: WO2006/122117,2006,A2 .Location in patent: Page/Page column 23
[2]Tetrahedron Letters,2002,vol. 43,p. 5965 - 5968
[3]Chemical Communications,2015,vol. 51,p. 2878 - 2881
[4]Organic Letters,2010,vol. 12,p. 3216 - 3218
[5]Chemistry - A European Journal,2019,vol. 25,p. 16550 - 16554
[6]Angewandte Chemie - International Edition,2017,vol. 56,p. 7078 - 7082
Angew. Chem.,2017,vol. 129,p. 7184 - 7188,5
[7]Journal of the American Chemical Society,2017,vol. 139,p. 3153 - 3160
[8]Angewandte Chemie - International Edition,2019,vol. 58,p. 592 - 595
Angew. Chem.,2019,vol. 131,p. 602 - 605,4
[9]Journal of Organic Chemistry,2007,vol. 72,p. 6618 - 6620
[10]Organic Letters,2005,vol. 7,p. 5191 - 5194
[11]Patent: WO2006/86562,2006,A2 .Location in patent: Page/Page column 252
[12]Journal of the American Chemical Society,2013,vol. 135,p. 2552 - 2559
[13]Patent: WO2006/102674,2006,A2 .Location in patent: Page/Page column 254-255; 284
[14]Patent: WO2006/122186,2006,A2 .Location in patent: Page/Page column 225
[15]Patent: WO2006/121861,2006,A2 .Location in patent: Page/Page column 181-182
[16]Patent: CN111004149,2020,A .Location in patent: Paragraph 0023-0026

4
[ 623-00-7 ]
[ 4187-87-5 ]
[ 68716-49-4 ]
4'-(3-oxo-3-phenyl-propenyl)-biphenyl-4-carbonitrile [ No CAS ]

Reference： [1]Synlett,2006,p. 3469 - 3473

5
[ 4187-87-5 ]
[ 68716-49-4 ]
(E)-1-phenyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)prop-2-en-1-one [ No CAS ]

Reference： [1]Synlett,2006,p. 3469 - 3473
[2]Journal of Medicinal Chemistry,2019,vol. 62,p. 3447 - 3474

6
[ 1001-53-2 ]
[ 68716-49-4 ]
[ 950201-41-9 ]

Yield	Reaction Conditions	Operation in experiment
		The reaction was carried out under N2 atmosphere. 4-Bromobenzeneboronic acid pina- col cyclic ester (300 mg, 1.06 mmol), 7V-acetylethylenediamine (0.155 ml, 1.59 mmol), Xantphos (123 mg, 0.21 mmol), and Cs2CO3 (518 mg, 1.59 mmol) were added to a mixture of 1,4-dioxane (5.88 ml) and DMF (0.12 ml) at room temperature, and N2 was fluxed through the mixture for 5 min. Pd(OAc)2 (24 mg, 0.1 mmol) was added and the mixture was irradiated under microwave conditions at 170 0C for 10 min into a sealed tube. The reaction was then cooled to room temperature and filtered through a pad of celited. The volatiles were evaporated in vacumm and the residues thus obtained was purified by short open column chromatography (SiO2, eluting with DCMZMeOH(NH3) to yield intermediate compound 8 (80 mg).

Reference： [1]Patent: WO2007/104783,2007,A2 .Location in patent: Page/Page column 41-42

7
[ 589-87-7 ]
[ 25015-63-8 ]
[ 99770-93-1 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
		[00367] 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 1-bromo-4-iodobenzene (242 mg; 0.855 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 monoborate at 8.8 minutes and the diborate at 13.7 minutes.

Reference： [1]Patent: US6680401,2004,B1 .Location in patent: Page column 57

8
[ 68716-49-4 ]
[ 121-45-9 ]
[ 852204-67-2 ]

Yield	Reaction Conditions	Operation in experiment
56%	With tris-(trimethylsilyl)silane; 1,1'-azobis(1-cyanocyclohexanenitrile); In toluene; at 105℃; for 4.5h;Product distribution / selectivity;	Crude 4-bromo-(4,4,5,5-tetramethyl- l,3,2-dioxaborolan-2-yl)benzene (20, 74.3g, 93.5%, 0.245 mol) was dissolved in toluene (300 mL, 0.82 M). To the solution was added trimethyl phosphite (94.0 mL, 0.797 mol) via funnel and the reaction was heated to 105C. A solution of 1,1'- Azobis-cyclohexane carbonitrile (ACBN, 9.8 g, 0.04 mol, alternatively, AIBN (2, T- azobisisobutyronitrile) can be used) and tris(trimethylsilyl) silane (97.2 mL, 0.315 mol) in toluene (200 mL) was added to the flask drop-wise over 4.5 hours at a rate of 1 mL/minute. Toluene was removed by distillation under vacuum, hexane (200 ml) was added and the reaction mixture was stirred at ambient temperature for 12 hours, then in an ice-water bath for 2 hours. The solid was filtered and washed with cold hexane EPO <DP n="25"/>Docket No. 2221.020AWO(150 niL), air dried, then vacuum dried to constant weight to afford dimethyl[4- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl]phosphonate (3, 46.0 g, 56% yield) as a light cream-colored crystalline solid. mp 84.2 + 0.8 C; R/ 0.29 (2:1 ethyl acetate-hexane); hplc 2.06 min; NMR purity >99 A%; 1H NMR (300 MHz, CDCl3) delta 7.89 (dd, J= 8.2, 4.6 Hz, 2H), 781 (dd, J= 13.2, 8.2 Hz, 2H), 3.75 (s, 3H), 3.72 (s, 3H), 1.34 (s, 12 H) ppm; MS [M+H] 312, [2M+H] 625.
	With 2,2'-azobis(isobutyronitrile); tris-(trimethylsilyl)silane;	In the scheme shown below is the description of a phosphonic acid containing compound. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (34A) to the corresponding pinacol ester 35A upon stirring with pinacol in toluene. Treatment of 35A with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produces the dimethylphosphonate derivative 36A in good yield. Suzuki coupling of 36A with 26A gives the expected biphenyl derivative that is deprotected by first hydrolysis in aqueous methanol and triethylamine, hydrogenolysis over palladium on carbon and finally treatment with bromotrimethylsilane to give the desired product 37A.
		Crude pinacol ester 20, synthesis described above, (210.Og, 0.742 mol) was dissolved in chlorobenzene (500 mL, 1.48 M), trimethyl phosphite (270.7 mL, 2.23 mol) was added via addition funnel and the reaction was heated to 110 0C. A solution of l,l'-azobis-cyclohexane carbonitrile (19.9 g, 0.082 mol) and tri-n-butyltin hydride (235.7 mL, 0.85 mol) in chlorobenzene (250 mL) was added drop-wise to the flask over 4.5 hours. The mixture was stirred for 1.5 hours at 110 0C then heating was discontinued, potassium fluoride (172.4g, 2.97 mol) and water (53.42 ml, 2.97 mol) were added and reaction was stirred overnight at ambient temperature. Sodium sulfate (50 g) was added and the mixture was filtered through a pad of Celite and sodium sulfate. The cake was washed with dichloromethane (2 x 750 ml) and the combined filtrates were concentrated under vacuum to obtain crude dimethyl[4-(4,4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl]phosphonate 3 as a yellow solid. A 3-L flask was charged with crude 3 (theory 0.742 mol) at room temperature. Anhydrous dichloromethane (740 ml) and bromotrimethylsilane (225.2 ml, 1.71 mol) were added in succession via additional funnel. The mixture was stirred at ambient temperature for 2 hours, then water (53.2 ml, 3.34 mol) was added and stirring was continued for another hour. The solvents were removed in vacuo to give the crude phosphonic acid 21 as a yellow colored solid. The crude product was recrystallized from tert-butyl methyl ether (750 mL) to give [4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl] phosphonic acid (21, 132.5 g, 63 % yield); 1H NMR (300 MHz, CD3OD) delta 7.72-7.87 (m, 4H), 1.35 (s, 12H) ppm.

	With 2,2'-azobis(isobutyronitrile); tris-(trimethylsilyl)silane;	[00247] In the scheme shown below is the description of a phosphonic acid containing compound. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (28) to the corresponding pinacol ester 29 upon stirring with pinacol in toluene. Treatment of 29 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produced the dimethylphosphonate derivative 30 in good yield.[00248] Suzuki coupling of 30 with 24 gives the biphenyl derivative 31. Catalytic hydrogenation of 31 over palladium on carbon removes the ben2yl protecting group and reduces the double bond to give ketone 32. Reduction of 32 with borane dimethylsulfide complex in the presence of a catalytic amount of tetrahydro-l-methyl-3,3-diphenyl-lH,3H- pyrrolo[l,2-c][l,3,2]oxazaborole, (R-CBS) followed by treatment with bromotrimethylsilane and an aqueous workup gives compound 33.; In the scheme shown below is the description of a phosphonic acid containing compound. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (28) to the corresponding pinacol ester 29 upon stirring with pinacol in toluene. Treatment of 29 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produced the dimethylphosphonate derivative 30 in good yield.
	With 2,2'-azobis(isobutyronitrile); tris-(trimethylsilyl)silane;	In the scheme shown below, the synthesis of a phosphonic acid compound is described. The sequence begins with the conversion of commercially available 4- bromophenylboronic acid (18) to the corresponding pinacol ester 19 upon stirring with pinacol in toluene. Treatment of 19 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane produces the dimethylphosphonate derivative 20 in good yield.[00267] Suzuki coupling of 20 with 9 gives the expected biphenyl derivative that is deprotected by hydrogenolysis over palladium on carbon and finally treatment with bromotrimethylsilane and aqueous HF treatment gives the desired product 21.
	With 2,2'-azobis(isobutyronitrile); tris-(trimethylsilyl)silane; In toluene;	2-Hydroxy-4-bromobenzaldehyde 4 was prepared by reaction of 3- bromophenol with paraformaldehyde in the presence of magnesium chloride and excess triethylamine in acetonitrile. Condensation of 4 with aniline (5) gave the desired imine 6a that was converted to the benzyl protected derivative 6b upon treatment with benzyl bromide and potassium carbonate in DMF. In the next step, 3b EPO <DP n="183"/>is treated with titanium tetrachloride and iV-ethyldiisopropylamine followed by treatment with 6b to effect enantiospecific condensation providing 7. Treatment of 7 with excess N,O-bistrimethylsilyl-acetamide followed by a catalytic amount of tetrabutylammonium fluoride hydrate results in ring closure to the desired beta-lactam (8) while maintaining the TBS protecting group on the benzylic alcohol. Commercially available 4-bromophenylboronic acid (9) is converted to the corresponding pinacol ester 10 by stirring with pinacol in toluene. Treatment of 10 with a mixture of trimethylphosphite, AIBN, and tris(trimethylsilyl)silane in toluene produces the dimethylphosphonate derivative 11 (an adaptation of the published procedure; Jiao, X. Y.; Bentrude, W. G. J Org. Chern. 2003, 68, 3303-3306). Suzuki coupling of 8 with 11 gives the expected biphenyl derivative 13 that is deprotected by hydrogenolysis over palladium on carbon, treatment with bromotrimethylsilane, and treatment with aqueous HF to give the product 12.

Reference： [1]Patent: WO2006/122117,2006,A2 .Location in patent: Page/Page column 23-24
[2]Patent: WO2006/86562,2006,A2 .Location in patent: Page/Page column 252
[3]Patent: WO2006/122117,2006,A2 .Location in patent: Page/Page column 29-30
[4]Patent: WO2006/102674,2006,A2 .Location in patent: Page/Page column 254-255; 284
[5]Patent: WO2006/122186,2006,A2 .Location in patent: Page/Page column 225
[6]Patent: WO2006/121861,2006,A2 .Location in patent: Page/Page column 181-182

9
[ 853955-69-8 ]
[ 68716-49-4 ]
[ 144432-80-4 ]

Yield	Reaction Conditions	Operation in experiment
81%		Example 7; Method for Preparing an Organic Compound by Using the Silicon-Based Cross-Coupling Reagent 2a of the Present Invention; As expressed by the following reaction formula (v), the silicon-based cross-coupling reagent 2a of the present invention was used to produce an organic compound p71 by carrying out a cross-coupling reaction between the silicon-based cross-coupling reagent 2a and an organic halide 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)bromobenzene (v1). In the present Example, first, BuLi (1.1 mol with respect to 1 mol of the silicon-based cross-coupling reagent 2a) was added to the silicon-based cross-coupling reagent 2a (1.5 mmol) in THF (1.1 mL) at -78 C., and the mixture was stirred, and the reaction solution was warmed gradually at room temperature. In this manner, lithium salt was made from the silicon-based cross-coupling reagent 2a.Next, DMF (0.4 mL) was added to the reaction solution, and a mixture of DMF and THF was used as a solvent. 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)bromobenzene (v1) (1.0 mmol) was added to a mixture of lithium salt of the silicon-based cross-coupling reagent 2a, [(eta3-allyl)PdCl]2 (1.5 mol % with respect to the organic halide), ligand as in Example 6 (6.3 mol % with respect to the organic halide), and CuI (3.0 mol % with respect to the organic halide) in the solvent, and the resulting mixture was stirred at 75 C. for 11 hours. The mixture was diluted with diethyl ether, and the resultant was washed with brine and then was dried over anhydrous MgSO4. After concentration with an evaporator, the residue was purified by flash chromatography on silica gel, thereby obtaining an organic compound p71 (yield of 81%).

Reference： [1]Patent: US2009/69577,2009,A1 .Location in patent: Page/Page column 24

10
[ 115-19-5 ]
[ 68716-49-4 ]
[ 1105663-20-4 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; at 110℃; for 0.333333h;	2-Methyl-but-3-yn-2-ol (24 ml; 247 mmol), 2-(4-bromo-phenyl)-4,4,5,5-tetramethyl- [1 ,3,2]dioxaborolane (8.7 g; 30.85 mmol) (J.Organomet. Chem. 2006, 691 (26), 5725), Pd(PPh3)2CI2 (4.33 g; 6.17 mol) CuI (1.17 g; 6.17 mmol) in DMF (140 ml) and triethylamine (60 ml) are heated to 1 100C for 20 minutes. The reaction mixture is evaporated to dryness and the residue taken up in hexanes/acetone (85:15), filtered and the filtrate purified via chromatography ((SiO2 ; hexanes/acetone 85:15) to deliver the target compound as light- brown crystals. 1 H-NMR (400MHz; DMSO-d6): 7.65 (d, 2H); 7.40 (d, 2H); 5.51 (s, 1 H); 1.48 (s, 6H); 1.31 (s, 12H). MS (m/z) ES+: 269 (100).

Reference： [1]Patent: WO2009/10488,2009,A1 .Location in patent: Page/Page column 58

11
[ 2978-58-7 ]
[ 68716-49-4 ]
[ 1105663-16-8 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; at 100℃; for 0.333333h;Microwave irradiation;	4-(4,4,5,5-Tetramethyl-1 ,3,2-dioxaborolan-2-yl)bromobenzene (J. Organomet. Chem. 2006, 691 (26), 5725) (200 mg; 0.71 mmol) 1 ,1-dimethyl-prop-2-ynylamine (350 mg; 4.25 mmol) Pd(PPh3)2CI2 (99 mg; 0.14 mmol) and CuI (27 mg; 0.14 mmol) are dissolved in DMF/NEt3 (3.5 ml/ 1.5 ml) and microwaved at 1000C for 20 minutes. The reaction mixture is evaporated and purified via chromatography (SiO2; TBME/ MeOH/M/NH3conc 95:5:0.8) to yield the title compound as yellowish crystals. H-NMR (400Hz; DMSO-d6): 7.64 (d, 2H); 7.38 (d, 2H); 2.08 (bs, 2H); 1.39 (s, 6H); 1.31 (s, 12H). MS (m/z) ES+: 285 (MH+).

Reference： [1]Patent: WO2009/10488,2009,A1 .Location in patent: Page/Page column 56

12
[ 589-87-7 ]
[ 73183-34-3 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
88%	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), bispinacolatodiboron (254 mg, 1 mmol, 2 equiv), and the appropriate aryl iodide (0.5 mmol). Under an argon atmosphere, freshly distilled DMSO (0.4 mL) and pyridine (0.4 to 1 equiv) were added successively using a syringe. The reaction mixture was heated to 105 C and stirred and stirred for 2 h under argon.
78%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 100℃;Inert atmosphere;	245 mg (0.30 mmoL) of PdCl2(dppf)2 and 3 g (30 mmoL) of KOAC are added to a flask, and the mixture is subjected to nitrogen flushing. Air in the flask is removed, and 2.9 g (10 mmoL) of 1 -bromo-4-iodobenzene and 60 mL of DMSO are added to the flask. The flask is placed in an oil bath and heated to 100 C. After the reaction is terminated, the resultant is subjected to extraction with MC and washed with H2O. The resultant is subjected to column chromatography to obtain Compound I (yield: 78%).

Reference： [1]Synthesis,2017,vol. 49,p. 4759 - 4768
[2]Patent: KR101594129,2016,B1 .Location in patent: Paragraph 0217-0222
[3]Journal of the American Chemical Society,2013,vol. 135,p. 18730 - 18733
[4]Angewandte Chemie - International Edition,2009,vol. 48,p. 5350 - 5354
Angew. Chem., Int. Ed.,2009,vol. 121,p. 5454 - 5458
[5]European Journal of Organic Chemistry,2014,vol. 2014,p. 1381 - 1385
[6]Journal of the American Chemical Society,2017,vol. 139,p. 607 - 610
[7]Organic Letters,2014,vol. 16,p. 4562 - 4565
[8]Journal of Organic Chemistry,2015,vol. 80,p. 9671 - 9681

13
[ 629-27-6 ]
[ 68716-49-4 ]
[ 378223-65-5 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 920 - 921
[2]Journal of the American Chemical Society,2010,vol. 132,p. 920 - 921

14
[ 106-40-1 ]
[ 73183-34-3 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
88%	With tert.-butylnitrite; eosin; In acetonitrile; at 20℃; for 2h;Irradiation;	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.
83%		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.
73%		General procedure: To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH(1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv) followed by H2O (0.5 ml). This mixture was stirred 2 min, and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg of NaNO2 in H2O (0.25 mL). This mixture was stirred 30 minat 0-5 C followed by B2pin2 (2, 381 mg, 1.5 mmol, 3.0equiv) in MeOH (1.0 mL). This mixture was stirred 60 min.H2O (10 mL) was added to the reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layers were washed with sat. NaHCO3, dried over Na2SO4, followed by evaporation, and the crude residue was purified by flash chromatography.

72%		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).
64%		The arylamine (10 mmol) was dissolved in a mixture of 5 mL of distilled water and 3:4 mL of 50% tetrafluoroboric acid. After cooling the reaction mixture to 0 C in an ice bath, sodium nitrite (0:69 g in 2 mL of distilled water ) was added dropwise within 5 min. The resulting mixture was stirred for 1 h, and the precipitate was collected by filtration and redissolved in the minimum amount of acetone. Diethyl ether was added until precipitation of the arenediazonium tetrafluoroborate, which was filtered, washed several times with diethylether, and dried under vacuum. An arenediazonium salt (1:5 mmol), bis(pinacolato)diborane(1 mmol) and PPh3 (2:0 eq.) were weighed in a 25 LSchlenk round bottom flask under nitrogen atmosphere. Then 3 mL of acetonitrile was added by syringe. The resulting solution was stirred at room temperature. The reaction progress was monitored by GC-MS. After the completion of the reaction,the solution was filtered though a short column of silica gel and the column washed with ethyl acetate. The filtrate was concentrated under reduced pressure to leave a crude product, which was purified by flash column chromatography on silica gel to afford the final products.

Reference： [1]Tetrahedron Letters,2016,vol. 57,p. 1551 - 1554
[2]Journal of Chemical Research,2018,vol. 42,p. 481 - 485
[3]Synlett,2014,vol. 25,p. 1577 - 1584
[4]Tetrahedron Letters,2017,vol. 58,p. 3851 - 3853
[5]Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences,2014,vol. 69,p. 982 - 986
[6]Journal of Organic Chemistry,2013,vol. 78,p. 1923 - 1933
[7]Synlett,2012,vol. 23,p. 1394 - 1396
[8]Angewandte Chemie - International Edition,2010,vol. 49,p. 1846 - 1849
[9]Angewandte Chemie - International Edition,2010,vol. 49,p. 1846 - 1849

15
[ 853955-69-8 ]
[ 68716-49-4 ]
[ 144432-80-4 ]
[ 321903-29-1 ]

Reference： [1]Bulletin of the Chemical Society of Japan,2010,vol. 83,p. 554 - 569

16
[ 37658-00-7 ]
[ 68716-49-4 ]
[ 1234215-31-6 ]

Reference： [1]Organic Letters,2010,vol. 12,p. 3216 - 3218

17
[ 24388-23-6 ]
[ 68716-49-4 ]
[ 269410-06-2 ]
[ 594823-67-3 ]

Reference： [1]Organic Letters,2010,vol. 12,p. 5474 - 5477

18
[ 2969-81-5 ]
[ 68716-49-4 ]
[ 2050-23-9 ]
[ 1365610-75-8 ]
[ 24388-23-6 ]
[ 105-54-4 ]
4,4′-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,1′-biphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With pyridine; 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; 1,10-Phenanthroline; NiI₂*3.5H₂O; sodium iodide; zinc at 20 - 60℃; for 20h; chemoselective reaction;

Reference： [1]Everson, Daniel A.; Jones, Brittany A.; Weix, Daniel J. [Journal of the American Chemical Society, 2012, vol. 134, # 14, p. 6146 - 6159]

19
[ 76-09-5 ]
[ 22092-92-8 ]
[ 673-40-5 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
65%		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 25: synthesis of 2-(4-bromophenyr)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [CAS 68716-49-4] , compound VIA22. 184 mg of 2-(3-iodophenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane were obtained following the general procedure D according to example 3, using 271 mg of 4-bromobenzenediazonium tetrafluoroborate as a pale yellow oil, with an isolated yield of 65%. 1H NMR (300 MHz, CDC13) delta 7.66 (d, J = 8.2 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 1.34 (s, 12H) nB NMR (100 MHz, CDC13) delta 31.04 13C NMR (75 MHz, CDC13) delta MS (EI) tR= 8.99 min; m/z: 283 (Mu+', 100%)

Reference： [1]Patent: WO2014/9169,2014,A1 .Location in patent: Page/Page column 64

20
[ 1401094-66-3 ]
[ 68716-49-4 ]
[ 1533422-46-6 ]

Yield	Reaction Conditions	Operation in experiment
16%	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

21
[ 108-86-1 ]
[ 76-09-5 ]
[ 1359224-18-2 ]
[ 68716-49-4 ]
[ 594823-67-3 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 2878 - 2881

22
[ 108-86-1 ]
[ 76-09-5 ]
[ 1350843-22-9 ]
[ 68716-49-4 ]
[ 594823-67-3 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 2878 - 2881

23
[ 108-86-1 ]
[ 76-09-5 ]
[ 2890-88-2 ]
[ 24388-23-6 ]
[ 68716-49-4 ]
[ 594823-67-3 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 2878 - 2881

24
[ 17763-67-6 ]
[ 68716-49-4 ]
[ 144432-80-4 ]

Reference： [1]Nature,2015,vol. 524,p. 454 - 457

25
[ 870-50-8 ]
[ 68716-49-4 ]
di-tert-butyl 1-(4-bromophenyl)hydrazine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	With water; copper diacetate; lithium tert-butoxide; In 1,2-dimethoxyethane; at 20℃;Inert atmosphere;	General procedure: To a 10-mL, two-necked flask (flask A) were added Cu(OAc)2 (4.5 mg, 0.025 mmol) and LiOt-Bu (60.0 mg, 0.75 mmol), and the atmosphere inside the flask was replaced with N2 by flushing (3 ×). To the flask, DME (0.5 mL) and H2O (4.5 muL, 0.025 mmol) were added and the mixture was stirred for over 15 min. To another 10-mL two-necked flask (flask B), arylboronic ester 1 (0.25 mmol) and di-tert-butyl azodicarboxylate (2, 115.1 mg, 0.5 mmol) were added, and after flushing the atmosphere in the flask with N2 (3 ×), DME (0.5 mL) was added. The solution in flask B was added to flask A via syringe within 1 min. Flask B was rinsed with DME (0.2 mL) and the solution was added to the flask A. After stirring for 13.5-16 h at r.t., the reaction was diluted with EtOAc (4 mL) and H2O (2-3 mL) and quenched with 1 M citric acid to neutralize the system. The organic layer was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel) to provide the hydrazine. Di-tert-butyl 1-(4-Bromophenyl)hydrazine-1,2-dicarboxylate (3d) [15]. White solid; yield: Table 1, entry 4: 72.4 mg (75%); Table 1, entry 14: 36.5 mg (38%); Rf = 0.31 (hexane-EtOAc, 5:1). 1H NMR (400 MHz, CDCl3): delta = 1.50 (s, 18 H), [6.65, 6.83 (br s, 1 H)], 7.32 (br, 2 H), 7.42 (d, J = 8.8 Hz, 2 H). 13C NMR (100 MHz, CDCl3): delta = 28.2, 28.3, 81.9, 82.8, 118.7, 125.1, 131.5, 141.4, 153.4, 155.5.

Reference： [1]Synthesis,2015,vol. 47,p. 3746 - 3750

26
[ 62-53-3 ]
[ 68716-49-4 ]
[ 54446-36-5 ]

Yield	Reaction Conditions	Operation in experiment
81%	With copper diacetate; triethylamine In methanol; acetonitrile at 80℃; for 24h; Molecular sieve; Sealed tube;

Reference： [1]Vantourout, Julien C.; Law, Robert P.; Isidro-Llobet, Albert; Atkinson, Stephen J.; Watson, Allan J. B. [Journal of Organic Chemistry, 2016, vol. 81, # 9, p. 3942 - 3950]

27
[ 110-89-4 ]
[ 68716-49-4 ]
[ 22148-20-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper diacetate; triethylamine In acetonitrile at 80℃; for 24h; Molecular sieve; Sealed tube;

Reference： [1]Vantourout, Julien C.; Law, Robert P.; Isidro-Llobet, Albert; Atkinson, Stephen J.; Watson, Allan J. B. [Journal of Organic Chemistry, 2016, vol. 81, # 9, p. 3942 - 3950]

28
[ 2915-16-4 ]
[ 68716-49-4 ]
2-(4-bromophenyl)-4,6-diphenylpyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 5h;Reflux;	In the Ar gas protection, in a 2000ml threeneckedflask 2_chlorodiphenylpyrimidine_4,6_ 26.6g (molecular weight266,0.1Omol), tons of friends on 4-bromophenylboronic acid pinacol ester 34g (molecular weight 282 , 0.12mol), tetrakis(triphenylphosphine) palladium6.0g (0.0052mol), 300ml of THF, 200ml of toluene, potassium carbonate 40g (molecular weight 138,0.29mol) was dissolvedin 200ml of water was added to the reaction flask. After repeated under reduced pressure ventilation, electric start stirring,the reaction was monitored by TLC (thin layer chromatography), after reflux 5h, the reaction was complete. Allowed to cool,the reaction system was divided into two layers, the organic layer was separated, evaporated to dryness, to obtain a solidproduct, which was recrystallized from toluene to give 27g of intermediate molecular weight 386, 70% yield.

Reference： [1]Patent: CN103570628,2016,B .Location in patent: Paragraph 0161-0164

29
[ 1262866-93-2 ]
[ 68716-49-4 ]
4-([1,1'-biphenyl]-4-yl)-2-(4-bromophenyl)quinazoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 120℃; for 3h;	4- (biphenyl-4-yl) -2-chloroquinazoline 10.0 g (31.6 mmol)andTo 9.8 g (34.7 mmol) of 2- (4-bromophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 200 mL of dioxane and 50 mL of distilled water were added. 1.8 g (1.6 mmol) of Pd (PPh3) 4 and 13.1 g (94.7 mmol) of K2CO3 were added, and the mixture was refluxed at 120 DEG C for 3 hours. The reaction mixture was cooled to room temperature and 500 mL of ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of E.A and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (10.8 g, yield 78%).

Reference： [1]Patent: KR2015/27443,2015,A .Location in patent: Paragraph 0111-0113

30
[ 1262866-93-2 ]
[ 68716-49-4 ]
C₄₆H₃₀N₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / 1,4-dioxane; water / 3 h / 120 °C 2: caesium carbonate; palladium diacetate; dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane / toluene / 12 h / 120 °C

Reference： [1]Current Patent Assignee: DOOSAN CORP. - KR2015/27443, 2015, A

31
[ 109-04-6 ]
[ 68716-49-4 ]
[ 63996-36-1 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; ethanol; water; for 0.333333h;Inert atmosphere; Heating;	522 microliters (?mul?) (5.30 mmoL) of 2-bromopyridine and 18 mg (0.159 mmoL) of Pd(PPh3)4 are dissolved in 15 mL of DME, and the mixture is subjected to nitrogen flushing. 1.5 g (5.3 mmoL) of Compound I and 15 mL of ethanol (EtOH) are added to the mixture, and Na2CO3 (2.0M in H2O, 8.0 mL) is added thereto. The mixture is bubbled with N2(g) for 20 minutes and heated. When the reaction is terminated, the resultant is subjected to a work-up procedure and column chromatography to obtain Compound J (yield: 78%).

Reference： [1]Patent: KR101594129,2016,B1 .Location in patent: Paragraph 0220; 0224-0225

32
[ 56181-49-8 ]
[ 68716-49-4 ]
2-(4-bromophenyl)-4,6-diphenylpyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 12h;	6.22 g (20 mmol) of 2-bromo-4,6-diphenylpyrimidine,4.24 g (15 mmol) of 2- (4-bromophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane,1.7 g (0.75 mmol) of Pd (PPh3) 4 and 6.3 g (45 mmol) of K2CO3 were dissolved in 300 mL of a THF / H2O solvent mixture (in a volume ratio of 2/1)The reaction solution was stirred at a temperature of 80 C for 12 hours.The resulting reaction solution was cooled to room temperature,The organic layer was extracted three times by using 60 mL of water and 60 mL of ethyl acetate.The organic layer thus collected was dried over magnesium sulfate, and the residue obtained by evaporating the solvent from the solvent was separated and purified by silica gel column chromatography,To obtain 4.4 g of intermediate I-7 (yield: 76%). The compounds thus produced were determined by using LC-MS.

Reference： [1]Patent: CN106565689,2017,A .Location in patent: Paragraph 0335; 0335; 0336; 0337; 0338

33
3-phenyl-6-chloroimidazo[1,2-a]pyrimidine [ No CAS ]
[ 68716-49-4 ]
3-phenyl-6-(4-bromophenyl)imidazo[1,2-a]pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95.64%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 1.5h;Inert atmosphere; Reflux;	The synthesis process is the same as above,Except that the starting material 3-bromo-6-chloro-imidazo [1,2-a] pyrimidine is used3-phenyl-6-chloroimidazo [1,2-c] pyrimidine,4-bromophenylboronic acid cleanyl ester instead of phenylboronic acid chelate ester as raw material,The remaining reagents did not change to give a pale yellow solid bromide.In a 500ml three bottles,With mechanical mixing, Ar gas protection,Was added 7.6 g of 3-bromo-6-chloroimidazo [1,2-a] pyrimidine (molecular weight: 231,0.033 mol)Knit the brows it phenylboronic acid ester 6.73 g (molecular weight 204,0.033mol),The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol)Aqueous sodium carbonate solution 100 ml (2M)Toluene 150ml, ethanol 100ml.Stirring reflux, monitoring reaction with TLC,After reaction for 1.5 hs, the reaction was complete.Cooled, separated, evaporated to dryness, separated by column chromatography, eluent with 1: 1 ethyl acetate: petroleum ether,To give 7.3 g of a slightly yellow solid compound,Purity 99.2%, yield: 95.64%.
83.2%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Reflux;	In a 1000ml three-necked flask, equipped with mechanical stirring, Ar gas protection, was added 3-phenyl-6-chloro-imidazo [1,2-a] pyrimidine 7.16 g (molecular weight 229,0.030mol), p-bromo boronic acid it knit the brows 9.1 g of ester (molecular weight 282,0.032mol), catalyst Pd (PPh3)4The amount of 1.8 g of (molecular weight 1154,0.001556mol), aqueous sodium carbonate solution 120ml (2M), toluene 300ml, ethanol 150ml.Was stirred at reflux, monitoring the reaction by TLC, the reaction was complete the reaction 3.5hs.Cooling, was separated, evaporated to dryness, the product was isolated by column chromatography eluted with 1: 3 ethyl acetate: petroleum ether to give 9.0g compound as a pale yellow solid, purity 97.0%, yield: 83.2%.
83.2%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Inert atmosphere; Reflux;	In a 1000ml three-necked flask, equipped with mechanical stirring, Ar gas protection, adding 3-phenyl-6-chloroimidazo [1,2-a] pyrimidine (7.16 g (molecular weight: 229, 0.030 mol), p-bromophenyl boronic acid pinacol ester 9.1 g (molecular weight: 282, 0.032 mol), catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol), 120 ml of a sodium carbonate aqueous solution (2M), 300 ml of toluene and 150 ml of ethanol. Stirring reflux, with TLC monitoring reaction, reaction 3.5hs after the reaction is complete. Cooled, separated, evaporated to dryness, using column chromatography The eluent was eluted with 1: 3 ethyl acetate: petroleum ether to give 9.0 g of a pale yellow solid having a purity of 97.0% and a yield of 83.2%.

83.2%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 3.5h;Inert atmosphere; Reflux;	In a 1000ml three-mouth bottle with mechanical stirring, Ar gas protection,Added 3-phenyl-6-chloroimidazo[1,2-a]pyrimidine 7.16 g (molecular weight 229, 0.030 mol),9.1 g of p-bromophenylboronic acid ester (molecular weight 282, 0.032 mol), 1.8 g of catalyst Pd(PPh3)4 (molecular weight 1154, 0.001556 mol), 120 ml (2 M) of sodium carbonate aqueous solution, 300 ml of toluene, and 150 ml of ethanol. The mixture was stirred at reflux and monitored by TLC. The reaction was complete after 3.5 hs. Cool, separate, and evaporate to dryness. The product was isolated by column chromatography. The eluent was washed with 1:3 ethyl acetate:petroleum ether to give 9.0 g of a pale yellow solid, 97.0% purity, yield: 83.2%.
	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 1.5h;Inert atmosphere; Reflux;	In a 500ml three-necked flask, with mechanical stirring, Ar gas protection,Join3-Bromo-6-chloroimidazo [1,2-a] pyrimidine7.6 g (molecular weight 231, 0.033 mol)benzeneBorate borate ester6.73 g (molecular weight 204, 0.033 mol)The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol), 100 ml of sodium carbonate aqueous solution (2M), 150 ml of toluene and 100 ml of ethanol. The mixture was stirred and refluxed, and the reaction was monitored by TLC. The reaction was complete after 1.5 hrs of reaction. The product was cooled down, separated off and evaporated to dryness. The product was isolated by column chromatography. The eluent was eluted with 1: 1 ethyl acetate: petroleum ether to give 7.3 g of a slightly yellow solid compound, purity 99.2%. Yield: 95.64%.

Reference： [1]Patent: CN104650117,2017,B .Location in patent: Paragraph 0088; 0089; 0090; 0091; 0092; 0093
[2]Patent: CN104650088,2017,B .Location in patent: Paragraph 0043-0045
[3]Patent: CN104650089,2017,B .Location in patent: Paragraph 0046; 0057-0059
[4]Patent: CN104650090,2018,B .Location in patent: Paragraph 0085-0087
[5]Patent: CN104650116,2017,B .Location in patent: Paragraph 0100; 0101; 0102; 0103; 0104; 0105

34
α-cumyl bromodifluoromethanesulfenate [ No CAS ]
[ 68716-49-4 ]
[ 81931-99-9 ]

Yield	Reaction Conditions	Operation in experiment
93%	With [(1,2-bis(diphenylphosphino)ethane)CuCl]; sodium t-butanolate; In toluene; at 50℃; for 2h;Glovebox; Sealed tube;	In the glove box, the DPPECuCl (25 mg, 10 muM %) and NaOt Bu (15 mg, 30 muM %) is added to the in tube sealing, and then adding 4-bromophenylboric acid pinacol ester (0.5 mmol, 1.0 equiv, 141 mg) and compound I - 1 (0.6 mmol, 1.2 equiv, 178 mg), 2 ml toluene, 50 C stirring 2 h. After the reaction, steaming and under reduced pressure, the residue passes through the rapid silica gel column chromatography, to obtain white solid 147 mg, yield 93%. After hydrogen spectrum identifying the purity of greater than 95%.

Reference： [1]Patent: CN107011219,2017,A .Location in patent: Paragraph 0100-0102
[2]Angewandte Chemie - International Edition,2019,vol. 58,p. 2413 - 2417
Angew. Chem.,2019,vol. 131,p. 2435 - 2439,5

35
[ 131222-99-6 ]
[ 68716-49-4 ]
C₃₀H₁₈Br₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 1.5h;Inert atmosphere; Reflux;	Synthesis in the same second step of Example 1,Except that one of the starting materials, 6-chloroimidazo [1,2-a] pyrimidine-3-borate,4-bromophenylboronic acid cleanyl alcohol instead of raw materials,The remaining reagents unchanged,Reaction for 1.5 hours,The reaction is complete,To give a white solid dibromo intermediate.The second step,In a 1000ml three bottles,With mechanical mixing, Ar gas protection,5,76 g of 6,12-dibromo Chrysene (molecular weight: 384, 0.015 mol) was added,The first step of the synthesis of 6-chloroimidazo [1,2-A] pyrimidine-3-boronic acid cleanyl ester 9.21g(Molecular weight: 279, 0.033 mol),The catalyst Pd (PPh3) 4 was used in an amount of 1.8 g (molecular weight 1154, 0.001556 mol)Aqueous sodium carbonate solution 120 ml (2M)Toluene 300ml, ethanol 150ml.Stirring reflux, with TLC monitoring reaction, a total reaction after 3.5hs complete reaction.Cooled, separated, evaporated to dryness, separated by column chromatography, eluent with 1: 1 ethyl acetate: petroleum ether,To give 6.7 g of a yellow solid compound having a purity of 97.0% and a yield of 81.2%.

Reference： [1]Patent: CN104650117,2017,B .Location in patent: Paragraph 0045; 0046; 0047; 0054; 0055; 0056

36
[ 131222-99-6 ]
[ 68716-49-4 ]
C₄₂H₂₄Cl₂N₆ [ No CAS ]

Reference： [1]Patent: CN104650117,2017,B

37
C₁₉H₁₃ClN₂ [ No CAS ]
[ 68716-49-4 ]
5-(4-bromophenyl)-1,2-diphenyl-1H-benzo[d]imidazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80.5%	With potassium phosphate; palladium diacetate; In water; N,N-dimethyl-formamide; at 130℃; for 10h;Inert atmosphere;	(3) In a 250 mL three-necked flask, nitrogen was introduced,0.02 mol of intermediate Y1 was added,120ml DMF,0.04 mol of phenylboronic acid,0.0002 moles of palladium acetate,After stirring, 0.02 mol of K3PO4 aqueous solution was added,Heated to 130 C,Reflux reaction 10 hours, sampling point plate, the reaction is complete. Natural cooling, extracted with 200ml methylene chloride, separated, the extract was dried over anhydrous sodium sulfate, filtered, the filtrate was steamed, purified by silica gel column,To give intermediate Z1, HPLC purity 99.5%, yield 80.5%.

Reference： [1]Patent: CN106946852,2017,A .Location in patent: Paragraph 0095; 0096; 0097

38
[ 74786-53-1 ]
[ 68716-49-4 ]
1-(4'-bromo-3-methoxybiphenyl-2-yl)-2-methylpropan-1-one [ No CAS ]

Reference： [1]Organic Letters,2017,vol. 19,p. 5940 - 5943

39
[ 1328064-88-5 ]
[ 68716-49-4 ]
C₂₆H₂₃BrN₂O [ No CAS ]

Reference： [1]ACS Catalysis,2017,vol. 7,p. 89 - 92

40
[ 2943-42-2 ]
[ 68716-49-4 ]
[ 22865-54-9 ]

Yield	Reaction Conditions	Operation in experiment
91.0%	With N,N,N,N,-tetramethylethylenediamine; copper(II) sulfate; cesium fluoride; In methanol; at 50℃; for 24h;Inert atmosphere;	General procedure: To a mixture of S-(4-(tert-butoxycarbonylamino)phenyl) 4-toluenethiosulfonate (2e) (94.8mg, 0.250 mmol, 1.0 equiv), copper sulfate (2.0 mg, 13 mumol, 5.0 mol %), and cesiumfluoride (77.2 mg, 0.508 mmol, 2.0 equiv) were added a solution of TMEDA (1.72 mg, 14.8mumol, 5.9 mol %) and phenylboronic acid pinacol ester (1c) (77.9 mg, 0.382 mmol, 1.5equiv) dissolved in MeOH (2.5 mL), and the mixture was stirred at 50 C for 24 h. Aftercooling to room temperature, the mixture was filtered through a pad of Celite, and then thefiltrate was concentrated under reduced pressure. To the residue was added EtOAc (20 mL)and the mixture was washed with aqueous saturated solution of sodium bicarbonate (20 mL ×2) and brine (20 mL), and then dried (Na2SO4). After filtration, the filtrate was concentratedunder reduced pressure. The residue was purified by preparative TLC (n-hexane/EtOAc =10/1) to give 4-(tert-butoxycarbonylamino)phenyl phenyl sulfide (3n) (61.9 mg, 0.205 mmol,82.2%) as a colorless solid. According to the procedure for preparing 4-(tert-butoxycarbonylamino)phenyl phenylsulfide (3n), 4-methoxycarbonylphenyl 4-tolyl sulfide (3a) (60.0 mg, 92.0%), 3-methoxyphenyl 4-tolyl sulfide (3b) (49.8 mg, 86.7%), phenyl 4-tolyl sulfide (3c) (40.1 mg,80.7%), 4-methoxyphenyl 4-tolyl sulfide (3d) (42.1 mg, 73.1%), 4-(dimethylamino)phenyl 4-tolyl sulfide (3e) (41.4 mg, 67.7%), 4-hydroxyphenyl 4-tolyl sulfide (3f) (36.0 mg, 66.5%), 4-bromophenyl 4-tolyl sulfide (3g) (62.8 mg, 91.0%), 2-bromophenyl 4-tolyl sulfide (3h) (62.8mg, 89.8%), 3-thienyl 4-tolyl sulfide (3i) (38.6 mg, 74.2%), (E)-2-(4-tolylthio)styrene (3j)(38.7 mg, 68.3%), diphenyl sulfide (3k) (34.0 mg, 72.8%), 4-methoxyphenyl phenyl sulfide(3l) (45.3 mg, 84.1%), 4-aminophenyl phenyl sulfide (3m) (5.0 mg, 50%), 4-chlorophenylphenyl sulfide (3o) (40.5 mg, 73.3%), 2-(benzamido)phenyl phenyl 4-toluenethiosulfonate(3p) (54.5 mg, 71.1%), 2-fluorophenyl phenyl 4-toluenethiosulfonate (3q) (40.9 mg, 80.6%),phenyl 3-thienyl sulfide (3r) (16.5 mg, 67.8%), and phenethyl phenyl sulfide (3s) (46.6 mg,86.5%) were prepared from the corresponding organoboronic acid pinacol esters 1 andthiosulfonates 2.

Reference： [1]Chemistry Letters,2018,vol. 47,p. 85 - 88

41
[ 993-52-2 ]
[ 68716-49-4 ]
trimethyl [4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]germane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With (o-hydroxyphenyl)diphenylphosphine; palladium diacetate; caesium carbonate; tetraethylammonium bicarbonate; In water; toluene; at 100℃; for 24h;Inert atmosphere; Glovebox;	General procedure: Conditions A: To a screw vial with a septum cap were added aryl bromide 1 (0.50 mmol), Pd(OAc)2 (11.2 mg, 0.05 mmol, 10 mol %), ligand 5 (27.8 mg, 0.10 mmol, 20 mol %), Cs2CO3 (195.5 mg, 0.60 mmol, 1.2 equiv), Et4NHCO3(9.5 mg, 0.05 mmol, 10 mol %), hexamethyldigermane (3; 120 muL, 0.60 mmol, 1.2 equiv), and toluene (1.25 mL) under argon atmosphere in a glove box. The vial was capped and removed from the glove box, and then H2O (1.25 mL) was injected via syringe. The vial was heated at 100 C for 24 h with stirring. After cooling to r.t., the organic layer was separated, and the aqueous layer was extracted with EtOAc (3 × 3 mL). The combined organic layers were washed with brine (3 mL) and dried (Na2SO4). After filtration and evaporation, purification of the crude product by silica gel column chromatography afforded the corresponding product 4.

Reference： [1]Synthesis,2018,vol. 50,p. 2067 - 2075

42
[ 3842-55-5 ]
[ 68716-49-4 ]
[ 23449-08-3 ]

Yield	Reaction Conditions	Operation in experiment
66%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 70℃; for 5h;	2.68 g (10 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine(2-chloro-4,6-diphenyl-[1,3,5]-triazine),2.82 g (10.0 mmol) of 4-bromo-phenylboronic acid pinacol ester(4-bromo-phenylboronic acid pinacol ester),0.58 g (0.5 mmol) of Pd(PPh3)4 and 4.14 g (30.0 mmol) ofK2CO3 was dissolved in 60 mL of a mixture of THF and H2O (2:1 by volume) to obtain a solution which was then stirred at 70C for about 5 hours.And then extracted three times with 60 mL of water and 60 mL of diethyl ether.The organic layer was collected and dried over magnesium sulfate to evaporate the solvent.The residue was separated and purified by silica gel column chromatography to obtain 2.56 of Intermediate I-7(yield: 66%).

Reference： [1]Patent: TWI614236,2018,B .Location in patent: Paragraph 0122; 0123

43
S-(trifluoromethyl)dimesitylsulfanium triflate [ No CAS ]
[ 68716-49-4 ]
[ 214360-65-3 ]

Reference： [1]Science,2018,vol. 360,p. 1010 - 1014

44
[ 1511-62-2 ]
[ 68716-49-4 ]
[ 1234319-14-2 ]

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 12543 - 12548
Angew. Chem.,2018,vol. 130,p. 12723 - 12728,6

45
[ 1197-22-4 ]
[ 68716-49-4 ]
C₁₃H₁₂BrNO₂S [ No CAS ]

Reference： [1]ACS Catalysis,2018,vol. 8,p. 9560 - 9566

46
[ 872705-64-1 ]
[ 68716-49-4 ]
C₃₆H₂₈Br₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Intermediate A (46.82 g, 100.08 mmol), 106-6 (28.31 g, 100.08 mmol), potassium carbonate (1.24 g, 9.00 mmol), toluene 200 mL were added to a 2 L reactor under a nitrogen atmosphere. Stir. The temperature in the reaction vessel was raised to 70 C, and Pd(PPh3) 4 (1.04 g, 0.90 mmol) was added thereto, and 100 mL of distilled water was stirred, and the mixture was stirred under reflux for 11 hours to sufficiently react. After the reaction was terminated by adding 70 mL of distilled water, the mixture was filtered under reduced pressure, and the solid was washed with distilled water, and then recrystallized from acetone, toluene, and THF to obtain a solid and then sublimed, and toluene was recrystallized to give compound 106-7; 46.56 g, yield 75%.
	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; for 8h;Inert atmosphere; Reflux;	Under an argon atmosphere, 33-6 (14.15 g, 50 mmol), intermediate A (22.55 g, 50 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (43 ml), aqueous sodium carbonate ( 2M, 21ml) was added to the flask, refluxing for 8 hours, cooled to room temperature, extracted with toluene, the organic phase was washed with saturated brine, and then dried, then purified by column chromatography to give compound 33-7; Under an argon atmosphere, 33-7 (30.90 g, 50 mmol), 33-8 (12.76 g, 50 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (43 ml), aqueous sodium carbonate ( 2M, 21ml) was added to the flask, and the reaction was refluxed for 8 hours, cooled to room temperature, extracted with toluene, and the organic phase was washed with brine. After drying the organic phase, it is purified by column chromatography to obtained compound 33, 26.86 g, yield of 75%.

Reference： [1]Patent: CN108727252,2018,A .Location in patent: Paragraph 0126-0128; 0131-0132
[2]Patent: CN108727260,2018,A .Location in patent: Paragraph 0090-0092; 0095; 0096

47
C₁₂H₆Br₂S₂ [ No CAS ]
[ 68716-49-4 ]
C₁₈H₁₀Br₂S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; potassium carbonate; tri tert-butylphosphoniumtetrafluoroborate; In water; at 20℃;Inert atmosphere;	Under the protection of nitrogen, weighed compound S6 (25mmol),S7 (25 mmol), [Pd2(dba)3]·CHCl3 (0.5 mmol)And HP(tBu)3·BF4 (1.0 mmol) was added to a 250 mL two-necked flask.Inject 100 mL of toluene into the two-necked flask (pre-pass N2 for 15 min to remove oxygen)Then, add 12mL of 1M K2CO3 aqueous solution dropwise (advance passN2 15min in addition to oxygen),Stir at room temperature overnight. After the reaction,Add 100 mL of deionized water and add a few drops of 2M HCl.Extracted with dichloromethane, the organic phase was collected and dried over anhydrous Na2SO4.The dried solution was filtered, and the solvent was removed on a rotary evaporator to give a crude product.The crude product was purified by silica gel column chromatography.Final purification gave solid S8 (20.5 mmol, yield 78%).

Reference： [1]Patent: CN109096246,2018,A .Location in patent: Paragraph 0099; 0100; 0101; 0102

48
[ 56075-37-7 ]
[ 73183-34-3 ]
[ 68716-49-4 ]

Yield	Reaction Conditions	Operation in experiment
60%	In acetonitrile; at 20℃; for 12h;UV-irradiation;	General procedure: A solution of arylazo sulfone 1 (0.10 mmol) and the respective diboron 2 (0.20 mmol, 2.00 equiv) in degassed MeCN (2.00 mL, 0.05 M) was poured into a glass vessel, capped, and exposed to blue light (H150 Kessil lamp, 34 W, 420 nm) at r.t. for 12 h. After the completion of the reaction (detected by TLC), the solvent was removed in vacuo and the crude product was purified via column chromatography on silica gel.

Reference： [1]Journal of Organic Chemistry,2018,vol. 83,p. 12831 - 12837
[2]Synthesis,2019,vol. 51,p. 1243 - 1252

49
[ 1403834-47-8 ]
[ 68716-49-4 ]
C₃₄H₄₈Br₂S₂Si₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; potassium carbonate; tri tert-butylphosphoniumtetrafluoroborate; In water; toluene; at 20℃;Inert atmosphere;	Under nitrogen protection, weighed compounds S8 (25 mmol), S9 (25 mmol), [Pd2(dba)3]·CHCl3 (0.5 mmol) and HP(tBu)3·BF4 (1.0 mmol), and added to 250 mL of two. In the flask. 100 mL of toluenewas injected into the two-necked flask(N215 min in addition to oxygen), and then 12 mL of a 1 Maqueous solutionof K2CO3 (previously introduced with N2 15 min for oxygen removal) wasadded dropwise, andstirred at room temperature overnight.After the reaction was over, 100 mL of deionized water was added and a few drops of 2M HCl were added dropwise.Extracted with dichloromethane, the organic phase was collected, and dried over anhydrous of Na2SO4 organic phase was dried.The dried organic phase was filtered, and thesolvent was removedusing a rotaryevaporator to give a crude product.The crude product was purified by silica gel column chromatography, to give a solid S10 (19.5 mmol,78%).

Reference： [1]Patent: CN109232598,2019,A .Location in patent: Paragraph 0094; 0116; 0117

50
7-bromo-3,6-dihexyl-9-(4-(hexyloxy)phenyl)-9H-thieno[2′,3':4,5]thieno [3,2-]thieno[2′,3':4,5]thieno [2,3-d]pyrrole-2-carbaldehyde [ No CAS ]
[ 68716-49-4 ]
C₄₃H₄₈BrNO₂S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran;Reflux;	General procedure: In a three-neck round-bottom flask was dissolved compound 5(353 mg, 0.25 mmol), borate ester 6 (286 mg, 0.5 mmol), K2CO3(1.25 mL, 2 M) and Pd(PPh3)4 (29 mg, 0.025 mmol) in THF (10 mL).The reaction mixture was stirred and heated at reflux overnight. Aftercooling to room temperature, water was added to quench the reaction.Then the solution was extracted thrice with ethyl acetate, the combinedorganic phase was separated and dried over anhydrous MgSO4. Afterthe solvent was evaporated, the remaining crude product was purifiedby column chromatography on silica gel to give the desired aldehyde 7as an orange solid (413 mg, 92% yield).

Reference： [1]Dyes and Pigments,2019,vol. 168,p. 1 - 11

51
[ 5765-65-1 ]
[ 68716-49-4 ]
C₁₄H₁₉BrN₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44%	With norborn-2-ene; palladium diacetate; potassium carbonate; In 1,4-dioxane; dimethyl sulfoxide; at 70℃; for 12h;Inert atmosphere;	To a reaction tube equipped with a magnetic stir bar was added the catalyst palladium acetate (4.5 mg, 0.02 mmol), potassium carbonate (110.4 mg, 0.8 mmol),Norbornene (37.6mg, 0.4mmol), 4-bromophenylboronic acid boric acid pinacol ester (84.6mg, 0.3mmol), 4-benzoate morpholinate (82.8mg, 0.4mmol),Dimethyl sulfoxide (0.8 mL) and 1,4-dioxane (2.0 mL),It was then heated to 70 C and reacted for 12 hours under an air-protective atmosphere. After the reaction was cooled to room temperature, the mixture was filtered through celite, washed with ethyl acetate,The filtrate was washed once with water, a saturated aqueous sodium chloride solution,The organic solvent is dried over Na2SO4, filtered,The solvent was removed under reduced pressure, and the compound I-29 was purified by column chromatography (colorless oily liquid, yield 44%).

Reference： [1]Chemical Science,2019,vol. 10,p. 8384 - 8389
[2]Patent: CN110357832,2019,A .Location in patent: Paragraph 0133-0135

52
[ 13994-57-5 ]
[ 68716-49-4 ]
2-(4-(3-methoxy-3-methylbut-1-yn-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; at 20℃; for 0.666667h;Inert atmosphere;	To a solution of 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17, 100 mg, 0.30 mmol) in Et3N (4 ml), PdCl2(PPh3)2 (43 mg, 0.30 mmol), CuI (12 mg, 0.061 mmol) and 3-methoxybut-1-yne (2, 30 mg, 0.30 mmol) were added, degassed with argon for 10 min and stirred at room temperature for 40 min. The reaction was diluted with hexane (10 ml) and filtered through a pad of celite and washed with hexane (10 mL) and concentrated in vacuo to give 2-(4-(3-methoxy-3-methylbut-1-yn-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (18, 80 mg, 88%) as a brown solid. MS (ESI -ve): 217

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2019,vol. 29

53
[ 535-13-7 ]
[ 68716-49-4 ]
[ 1228690-28-5 ]

Reference： [1]Angewandte Chemie - International Edition,2019,vol. 58,p. 14584 - 14588
Angew. Chem.,2019,vol. 131,p. 14726 - 14730,5

54
[ 68716-49-4 ]
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenesulfonyl fluoride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%		A reaction tube was charged with 4-bromophenylboronic acid pinacol ester (85 mg, 0.30 mmol, 1.0 equiv), DABSO (72 mg, 0.30 mmol, 1.0 equiv) and PdCl2(AmPhos)2 (10.6 mg, 0.015 mmol, 5.0 mol %), sealed with a rubber septum, evacuated and back-filled with N2 three times. Anhydrous degassed isopropanol (1.2 mL) and anhydrous triethylamine (0.13 mL, 0.90 mmol, 3.0 equiv) were added subsequently, and the reaction mixture was stirred under positive pressure of N2 in a preheated aluminium heating block at 75 C for 24 h. After cooling to ambient temperature, NFSI (104 mg, 0.33 mmol, 1.1 equiv) was added. The reaction mixture was stirred at ambient temperature for 3 h until completion. The reaction mixture was then diluted with EtOAc, filtered through a plug of Celite and concentrated in vacuo to yield the crude product which was then purified by flash column chromatography (10-30% EtOAc in petrol), affording the sulfonyl fluoride 2a as a white solid (57 mg), 67 % yield.

Reference： [1]Tetrahedron,2020,vol. 76

55
[ 536-74-3 ]
[ 68716-49-4 ]
[ 1190376-20-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; for 22h; Inert atmosphere; Schlenk technique;

Reference： [1]Eisele, Pascal; Ullwer, Franziska; Scholz, Sven; Plietker, Bernd [Chemistry - A European Journal, 2019, vol. 25, # 72, p. 16550 - 16554]

56
[ 1873-77-4 ]
[ 292638-85-8 ]
[ 68716-49-4 ]
C₂₅H₄₉BO₄Si₄ [ No CAS ]

Reference： [1]ACS Catalysis,2020,vol. 10,p. 777 - 782

57
[ 2432-51-1 ]
[ 68716-49-4 ]
[ 190788-58-0 ]

Reference： [1]Chemical Science,2020,vol. 11,p. 2187 - 2192

58
N-(2,6-diisopropylphenyl)-N-(pyridine-2-yl)benzamide [ No CAS ]
[ 68716-49-4 ]
C₂₄H₂₅BrN₂O [ No CAS ]

Reference： [1]ACS Catalysis,2020,vol. 10,p. 3398 - 3403

59
[ 15790-87-1 ]
[ 68716-49-4 ]
methyl 3-(4-bromophenyl)pentanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48.6%	With (R)-(+)-2,2?-bis(diphenylphosphino)-1,1?-binaphthalene; chlorobis(ethylene)rhodium(I) dimer; sodium hydroxide; In 1,4-dioxane; at 20℃; for 12h;Inert atmosphere;	To a stirred solution of 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 21.20 mmol) in 1,4-Dioxane (60 ml) were added sodium hydroxide (19.08 mL, 19.08 mmol), argon gas was purged for 15 mins. Then added (E)-methyl pent-2-enoate (2.420 g, 21.20 mmol), chlorobis(ethylene)rhodium(I) dimer (0.124 g, 0.318 mmol) and (R)-(+)-2,2?-bis(diphenyl phosphino)-1,1?-binaphthyl (0.290 g, 0.466 mmol) at room temperature. Argon gas was purged for 5 min. The reaction tube was screw-capped and stirred at room temperature for 12 h. The reaction mixture was quenched with acetic acid (1.214 mL, 21.20 mmol), stirred for 5 mins and diluted with water (100 mL). The aqueous layer was extracted with ethyl acetate (3×100 mL). The combined organic layer was washed with water (50 mL), brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to afford the crude material, which was purified by flash silica gel column chromatography to afford 58A (brown oil, 4.5 g, 16.6 mmol, 48.6%). LC-MS Anal. Calc'd for C12H16BrNO2 270.0, found [M+3] 273.0, Tr=2.170 min (Method BB).

Reference： [1]Patent: US2020/69646,2020,A1 .Location in patent: Paragraph 0433

60
[ 13168-99-5 ]
[ 68716-49-4 ]
methyl 3-(4-bromophenyl)-4-methoxybutanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With (R)-(+)-2,2?-bis(diphenylphosphino)-1,1?-binaphthalene; chlorobis(ethylene)rhodium(I) dimer; sodium hydroxide; In 1,4-dioxane; at 20℃; for 12h;Inert atmosphere;	59A Enantiomer 2. methyl 3-(4-bromophenyl)-4-methoxybutanoate (Absolute Stereochemistry not Determined) To a stirred solution of 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5 g, 17.67 mmol) in 1,4-Dioxane (60 mL) were added sodium hydroxide (15.90 mL, 15.90 mmol). Argon gas was passed through the mixture for 15 mins. Then added (E)-methyl 4-methoxybut-2-enoate (4.60 g, 35.3 mmol), chlorobis(ethylene)rhodium(I) dimer (0.103 g, 0.265 mmol) and (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.242 g, 0.389 mmol) at room temperature. Argon gas was passed through it for another 5 mins. The reaction mixture was screw-capped and stirred at room temperature for 12 h. The reaction suspension was quenched with acetic acid (1.012 mL, 17.67 mmol), stirred for 5 min and diluted with water (100 mL). The aqueous layer was extracted with ethyl acetate (3*100 mL). The combined organic layer was washed with water (50 mL), brine (50 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to afford the crude material, which was purified by flash silica gel column chromatography to afford 59A (yellow oil, 3.6 g, 10.03 mmol, 80% yield). 1H NMR (400 MHz, CD3OD) delta 7.42-7.46 (m, 2H), 7.18-7.21 (m, 2H), 3.75 (s, 3H), 3.48-3.53 (m, 3H), 3.34 (s, 3H), 2.79-2.87 (m, 1H), 2.57-2.65 (m, 1H).

Reference： [1]Patent: US2020/69646,2020,A1 .Location in patent: Paragraph 0443; 0453

61
diethyl 4-[(2S)-1-methoxy-1-oxopropan-2-yl]carbamoyl}-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate [ No CAS ]
[ 68716-49-4 ]
methyl [4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoyl]-L-alaninate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2020,vol. 59,p. 5248 - 5253
Angew. Chem.,2020,vol. 132,p. 5286 - 5291,6

62
[ 15790-87-1 ]
[ 68716-49-4 ]
methyl (R)-3-(4-bromophenyl)pentanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62.6%		To a stirred solution of 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 21.20 mmol) in 1,4-Dioxane (60 mL) were added sodium hydroxide (19.08 mL, 19.08 mmol). To this argon gas was bubbled through the mixture for 15 mins and then (E)-methyl pent-2-enoate (2.420 g, 21.20 mmol), chlorobis(ethylene)rhodium(I) dimer (0.124 g, 0.318 mmol) and (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.290 g, 0.466 mmol) were added at room temperature. Then the Argon gas was bubbled through it for 5 mins. Then the reaction mixture was stirred at room temperature for 12h in a sealed tube. The reaction mixture was cooled to room temperature, quenched with acetic acid (1.214 mL, 21.20 mmol), stirred for 5 mins and diluted with water (100 mL). The aqueous layer was extracted with ethyl acetate (3*100 mL). The combined organic layer was washed with water (50 mL), brine (50 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to afford the crude sample. The crude was purified by flash silica gel column chromatography to afford 125A (yellow oil, 3.6 g, 13.28 mmol, 62.6% yield). 1H NMR data: 400 MHz, CD3OD: delta 7.43-7.46 (m, 2H), 7.13-7.16 (m, 2H), 3.72 (s, 3H), 2.95-2.99 (m, 1H), 2.67-2.73 (m, 1H), 2.54-2.60 (m, 1H), 1.61-1.75 (m, 2H), 0.80 (t, J=7.20 Hz, 3H).

Reference： [1]Patent: US2020/69695,2020,A1 .Location in patent: Paragraph 0553

63
[ 624-38-4 ]
[ 68716-49-4 ]
[ 17788-94-2 ]

Yield	Reaction Conditions	Operation in experiment
54%		Compound 1-D (34.8 g, 105.4 mmol, 1.0 eq) and compound 1-E (59.7 g, 211 mmol, 2.0 eq) were dissolved in THF (210 g) and stirred in a water bath at 50 C. for 10 minutes.K2CO3 (72.84 g, 527 mmol, 5.0 eq) was dissolved in water (500 mL) and added dropwise over 10 minutes. Pd(dppf)2Cl2 (2.34 g, 3.2 mmol, 0.03 eq) was added at 50 C. After stirring at 50 C. for 1 hour, the was separated by organic layer washing with ethyl acetate / water and the solvent was dried under vacuum.After purification by column chromatography with n-hexane and ethyl acetate, recrystallization with THF and ethanol,A white solid, compound 2-D (22.1 g), was obtained.

Reference： [1]Patent: KR2020/29344,2020,A .Location in patent: Paragraph 0189-0193

64
[ 162715-91-5 ]
[ 68716-49-4 ]
C₃₀H₃₆Br₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48%		Compound 1-F (52.5 g, 105.4 mmol, 1.0 eq) and compound 1-E (59.7 g, 211 mmol, 2.0 eq) were dissolved in THF (320 g) and stirred in a water bath at 50 C. for 10 minutes. K2CO3 (72.84 g, 527 mmol, 5.0 eq) was dissolved in water (500 mL) and added dropwise over 10 minutes. Pd(dppf)2Cl2 (2.34 g, 3.2 mmol, 0.03 eq) was added at 50 C. After stirring at 50 C. for 1 hour, the organic layer was separated by washing with ethyl acetate / water and the solvent was dried under vacuum.After purification by column chromatography with n-hexane and ethyl acetate, recrystallization with THF and ethanol afforded the compound 2-F (28.15 g) as a white solid.

Reference： [1]Patent: KR2020/29344,2020,A .Location in patent: Paragraph 0203-0207

65
C₂₂H₂₀BO₂^(1-)*Li⁽¹⁺⁾ [ No CAS ]
[ 68716-49-4 ]
[ 214360-66-4 ]
8,9-dioxa-8a-borabenzo[fg]tetracene [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2020,vol. 142,p. 9938 - 9943

66
[ 25999-04-6 ]
[ 68716-49-4 ]
N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)morpholine-4-sulfamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With nickel(II) bromide dimethoxyethane; (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; 1,8-diazabicyclo[5.4.0]undec-7-ene; 4,4'-di-tert-butyl-2,2'-bipyridine In ethanol at 30℃; for 72h; Microwave irradiation; Inert atmosphere; Sealed tube;

Reference： [1]Simons, R. Thomas; Scott, Georgia E.; Kanegusuku, Anastasia Gant; Roizen, Jennifer L. [Journal of Organic Chemistry, 2020, vol. 85, # 10, p. 6380 - 6391]

67
[ 52088-10-5 ]
[ 68716-49-4 ]
3-(4-bromophenyl)-1-methyl-1H-indazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine In toluene at 90℃; for 5h;	1 Take reactant II-4 (774mg, 3mmol)With p-bromophenylboronic acid pinacol ester (933mg, 3.3mmol),DIEA (5mmol) was added to 10mL toluene,Heat to 90°C to keep warm and react for 5 hours.After the reaction is complete, the solvent is distilled off under reduced pressure,Dry under vacuum to obtain Intermediate II-4 (off-white solid, 689mg);

Reference： [1]Current Patent Assignee: C P PREMIX TIANJIN - CN111925329, 2020, A Location in patent: Paragraph 0019

68
[ 127-19-5 ]
[ 68716-49-4 ]
[ 1421341-01-6 ]

Yield	Reaction Conditions	Operation in experiment
75%	With 2,6-dimethylpyridine; [2,2]bipyridinyl; nickel(II) bromide dimethoxyethane at 30℃; for 48h; Inert atmosphere; Irradiation; regioselective reaction;

Reference： [1]Das, Saikat; Murugesan, Kathiravan; Villegas Rodríguez, Gonzalo J.; Kaur, Jaspreet; Barham, Joshua P.; Savateev, Aleksandr; Antonietti, Markus; König, Burkhard [ACS Catalysis, 2021, vol. 11, # 3, p. 1593 - 1603]

69
[ 529-28-2 ]
[ 68716-49-4 ]
[ 881314-65-4 ]
[ 4877-93-4 ]

Yield	Reaction Conditions	Operation in experiment
58%	With bis(tri-tert-butylphosphine)palladium⁽⁰⁾; (C₅H₅)2Zr(OC₄H₈)N(Si(CH₃)3)CH(C₆H₅); tri-tert-butyl phosphine In toluene at 80℃; for 16h; Sealed tube; Inert atmosphere;

Reference： [1]Fu, Yue; Liu, Fang-Jie; Liu, Peng; Tang, Jian-Tao; Toste, F. Dean; Wu, Ting-Feng; Ye, Baihua; Zhang, Yue-Jiao [Chem, 2021, vol. 7, # 7, p. 1963 - 1974]

70
[ 1002-28-4 ]
[ 68716-49-4 ]
C₁₈H₂₅BO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With tetrabutylammomium bromide; Ni(dtbbpy)<SUB>3</SUB>Cl<SUB>2</SUB>; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl acetamide at 20℃; for 8h; Inert atmosphere; Electrochemical reaction; Molecular sieve; Sealed tube; chemoselective reaction;

Reference： [1]Zhang, Hai-Jun; Chen, Longrui; Oderinde, Martins S.; Edwards, Jacob T.; Kawamata, Yu; Baran, Phil S. [Angewandte Chemie - International Edition, 2021, vol. 60, # 38, p. 20700 - 20705][Angew. Chem., 2021, vol. 133, # 38, p. 20868 - 20873]

71
[ 109-86-4 ]
[ 68716-49-4 ]
[ 959972-40-8 ]

Yield	Reaction Conditions	Operation in experiment
47%	With tetrabutylammomium bromide; Ni(dtbbpy)<SUB>3</SUB>Cl<SUB>2</SUB>; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl acetamide at 20℃; for 8h; Inert atmosphere; Electrochemical reaction; Molecular sieve; Sealed tube; chemoselective reaction;

72
[ 20691-89-8 ]
[ 68716-49-4 ]
1-methyl-4-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenoxymethyl]-piperidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46%	With tetrabutylammomium bromide; Ni(dtbbpy)<SUB>3</SUB>Cl<SUB>2</SUB>; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl acetamide at 20℃; for 8h; Inert atmosphere; Electrochemical reaction; Molecular sieve; Sealed tube; chemoselective reaction;

73
tris(phenylethynyl)indium [ No CAS ]
[ 68716-49-4 ]
[ 1190376-20-5 ]

Yield	Reaction Conditions	Operation in experiment
81%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In tetrahydrofuran at 80℃; for 16h; Inert atmosphere;

Reference： [1]Jayasundara, Chathurika R. K.; Gil-Negrete, José M.; Montero Bastidas, Jose R.; Chhabra, Arzoo; Martínez, M. Montserrat; Pérez Sestelo, José; Smith, Milton R.; Maleczka, Robert E. [Journal of Organic Chemistry, 2022, vol. 87, # 1, p. 751 - 759]

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H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 68716-49-4 ] {[proInfo.proName]}

Quality Control of [ 68716-49-4 ]

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[ 68716-49-4 ] Synthesis Path-Upstream 1~6

[ 68716-49-4 ] Synthesis Path-Downstream 1~73

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Organoboron

Aryls

Bromides

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[ 68716-49-4 ]