[ CAS No. 916587-44-5 ] {[proInfo.proName]}

Name: 916587-44-5|tert-Butyl methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate|96%
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SKU: A317269
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Product Details of [ 916587-44-5 ]

CAS No. :	916587-44-5	MDL No. :	MFCD03490498
Formula :	C₁₈H₂₈BNO₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	MWNMXMKLILKYOS-UHFFFAOYSA-N
M.W :	333.23	Pubchem ID :	4712653
Synonyms :

Safety of [ 916587-44-5 ]

Signal Word:	Warning	Class:
Precautionary Statements:	P261-P272-P273-P280-P302+P352-P333+P313-P363-P501	UN#:
Hazard Statements:	H317-H413	Packing Group:
GHS Pictogram:

Application In Synthesis of [ 916587-44-5 ]

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

Downstream synthetic route of [ 916587-44-5 ]

[ 916587-44-5 ] Synthesis Path-Downstream 1~43

1
[ 916587-44-5 ]
[ 1014613-05-8 ]
[ 1014613-23-0 ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium carbonate In 1,4-dioxane; water at 150℃; for 0.5h; Microwave irradiation;	4-Bromo-2-methyl-1-(phenylsulfonyl)-1H-pyrrolo[2,3-6]pyridine (0.100g, 0.284mmol) 1,1- dimethylethyl methyl[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate (0.144g, 0.427mmol), bis(diphenylphosphino)ferrocene palladium (II) chloride (0.023g, 0.0284mmol) and sodium carbonate (0.09Og, 0.852mmol) in dioxan (3.5ml) and water (0.7ml) were heated in the Biotage Initiator mw at 150°C for 30 min. The reaction mixture was partitioned between DCM (10ml) and saturated citric acid : water (1:2, 15ml). The aqueous phase was extracted with DCM (10ml). The combined organic extracts were concentrated and the dark residue purified by FlashMaster on silica using EtOAc - cyclohexane (0-100%). The desired fractions were combined and concentrated in vacuo to give the title compound as a white solid (0.132g, 97%). MH+478, rt= 1.41 min

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2008/34860, 2008, A1 Location in patent: Page/Page column 122

2
[ 73183-34-3 ]
[ 306768-12-7 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
63%	With potassium acetate In dimethyl sulfoxide at 80℃; for 3.5h;
63%	With CH₃COOK; PdCl₂(Fe(C₅H₄P(C₆H₅)2)2)*CH₂Cl₂ In dimethyl sulfoxide (N2); addn. of soln. of carbamic acid deriv. in DMSO to mixture of boroncompd., palladium compd. and potassium acetate, stirring at 80°C for 3.5 h; cooling to room temp., addn. of ethyl acetate, washing with water, drying with MgSO4, concn., chromy. (silica gel, hexanes/ethyl acetate (8:1)),NMR;

Reference： [1]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]
[2]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]

3
[ 916587-44-5 ]
[ 926622-39-1 ]
3-{3-[4'-(tert-butoxycarbonylmethylamino)biphenyl-3-ylsulfanyl]benzyl}-3H-imidazole-4-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With potassium carbonate In 1,2-dimethoxyethane at 80℃; for 24h;

Reference： [1]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]

4
[ 916587-44-5 ]
3-{3-[4'-(tert-butoxycarbonylmethylamino)biphenyl-3-ylsulfanyl]benzyl}-3H-imidazole-4-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 63 percent / K₂CO₃ / PdCl₂(dppf)*CH₂Cl₂ / 1,2-dimethoxy-ethane / 24 h / 80 °C 2: 93 percent / NaOH / methanol; H₂O / 24 h / 20 °C

Reference： [1]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]

5
[ 916587-44-5 ]
3-[3-(4'-methylaminobiphenyl-3-ylsulfanyl)benzyl]-3H-imidazole-4-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 63 percent / K₂CO₃ / PdCl₂(dppf)*CH₂Cl₂ / 1,2-dimethoxy-ethane / 24 h / 80 °C 2: 99 percent / CF₃COOH / CH₂Cl₂ / 2 h / 20 °C

Reference： [1]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]

6
[ 916587-44-5 ]
C₂₉H₂₈ClN₃O₃S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 63 percent / K₂CO₃ / PdCl₂(dppf)*CH₂Cl₂ / 1,2-dimethoxy-ethane / 24 h / 80 °C 2: 93 percent / NaOH / methanol; H₂O / 24 h / 20 °C 3: DMF / CH₂Cl₂; toluene / 1 h / 0 °C

Reference： [1]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]

7
[ 916587-44-5 ]
3-(3-{4'-[(3-{3-[4'-(tert-butoxycarbonylmethylamino)biphenyl-3-ylsulfanyl]benzyl}-3H-imidazole-4-carbonyl)methylamino]biphenyl-3-ylsulfanyl}benzyl)-3H-imidazole-4-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 63 percent / K₂CO₃ / PdCl₂(dppf)*CH₂Cl₂ / 1,2-dimethoxy-ethane / 24 h / 80 °C 2: 93 percent / NaOH / methanol; H₂O / 24 h / 20 °C 3: DMF / CH₂Cl₂; toluene / 1 h / 0 °C 4: 0.94 g / pyridine; CH₂Cl₂ / 20 °C
	Multi-step reaction with 3 steps 1: 63 percent / K₂CO₃ / PdCl₂(dppf)*CH₂Cl₂ / 1,2-dimethoxy-ethane / 24 h / 80 °C 2: 99 percent / CF₃COOH / CH₂Cl₂ / 2 h / 20 °C 3: 0.94 g / pyridine; CH₂Cl₂ / 20 °C

8
[ 24424-99-5 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 83 percent / Et₃N; DMAP / CH₂Cl₂ / Heating 2: 63 percent / KOAc / PdCl₂(dppf)*CH₂Cl₂ / dimethylsulfoxide / 3.5 h / 80 °C
	Multi-step reaction with 3 steps 1.1: <i>tert</i>-butyl alcohol / 24 h / 40 °C / Inert atmosphere 2.1: sodium hydride / N,N-dimethyl-formamide; tetrahydrofuran; mineral oil / 0.5 h / 0 °C / Inert atmosphere 2.2: 12 h / 0 - 20 °C / Inert atmosphere 3.1: tricyclohexylphosphine; [Rh(OH)(cod)]2 / hexane / 1 h / 80 °C / Glovebox; Inert atmosphere 3.2: 12 h / 80 °C / Glovebox; Inert atmosphere

Reference： [1]Lin, Chen; Drueckhammer, Dale G. [New Journal of Chemistry, 2006, vol. 30, # 12, p. 1725 - 1730]
[2]Uetake, Yuta; Niwa, Takashi; Hosoya, Takamitsu [Organic Letters, 2016, vol. 18, # 11, p. 2758 - 2761]

9
[ 60577-34-6 ]
[ 916587-44-5 ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 1725 - 1730

10
[ 916587-44-5 ]
[ 894772-82-8 ]
tert-butyl N-methyl-N-[4-(4,4-dioxo-4-thia-2,5,9-triaza-1(2,4)-pyrimidina-3(1,3)-benzenacyclononaphan-1⁵-yl)phenyl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In N,N-dimethyl-formamide at 20 - 100℃; for 2h;	1 (Typical Scale: 0.25 mmol) A solution of the respective macrocyclic halide in DMF (8 mL per mmol halide) was treated with the respective organoboron compound (1.25 eq.), K2CO3 (2.5 eq., either as a solid or as 2 M aqueous solution), and POPd (2.5-5 mol-%) at room temperature. The stirred resulting mixture was placed into an oil bath preheated to 100° C. The reaction progress was monitored by TLC, and in case of incomplete turnover of the macrocyclic halide after 2 h additional portions of POPd and the organoboron compound were added followed by additional stirring at 100° C. After cooling to room temperature, water was added and the resulting suspension was stirred for 30 min. The crude product was isolated by vacuum filtration, dried in vacuo, and purified by column chromatography, followed optionally by trituration with methanol and/or preparative HPLC (e.g. YMC Pro C18RS 5μ, 150×20 mm, 0.2% NH3 in water/acetonitrile) to yield the analylically pure products. Alternatively, after full conversion the reaction mixture was diluted with ethyl acetate, quenched with water. Layers were separated, the organic layer was extracted with ethyl acetate twice and the combined organic layers dried and concentrated in vacuo followed by the above mentioned further purification steps.; Intermediate 10 was prepared according to GP 1 from 15-iodo-4-thia-2,5,9-triaza-1(2,4)-pyrimidina-3(1,3)-benzenacyclononaphan-4,4-dioxide and tert-butyl N-methyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate. 1H-NMR (DMSO, 400 MHz): 9.58 (s, 1H); 9.42 (s, 1H); 7.77 (s, 1H); 7.73 (t br, 1H); 7.31-7.38 (m, 5H); 7.26 (t br, 2H); 6.95 (t br, 1H); 3.32-3.44 (m, 2H); 3.20-3.28 (m, 2H); 3.18 (s, 3H); 1.74-1.87 (m, 2H); 1.38 (s, 9H). MS (ESI): [M+H]+=511.

Reference： [1]Current Patent Assignee: BAYER AG - US2006/167030, 2006, A1 Location in patent: Page/Page column 9-10; 13-14

11
[ 916587-44-5 ]
[ 10397-13-4 ]
[ 1155306-49-2 ]

Yield	Reaction Conditions	Operation in experiment
		Example 13 N-[4-(2>-Amino-2-morpholin-4-vH4,5'lbipyrimidinvI-6-yl)- phenyll-N-methyl-methanesulfonamide (56) Standard Suzuki reaction betwen Intermediate Al and t-butyl-N-methyl-N-[4-(tetramethyldioxaboronyl)phenyl]carbamate yielded [4-(6-chloro-2-morpholm-4-yl- pyrimidin-4-yl)-phenyl]-methyl-carbamic acid tert-butyl ester. Cleavage of the BOC grup using HCl in ether yielded [4-(6-chloro-2-morpholin-4-yl-pyrimidin-4-yl)-phenyl]- methyl-amine.Reaction of [4-(6-chloro-2-morpholin-4-yl-pyrimidin-4-yl)-phenyl]-methyl- amine with methane sulphonyl chloride in dichloromethane using triethylamine as base yielded N-[4-(6-chloro-2-mophiholin-4-yl-pyrimidin-4-yl)-phenyl]-N-methyl- methanesulfonamide. <n="96"/>Reaction of N-[4-(6-chloro-2-mthetaphiholin-4-yl-pyrimidin-4-yl)-phenyl]-N- methyl-methanesulfonamide with 2-aminopyrimidine-5-boronic acid, pinacol ester using standard Suzuki conditions yielded the desired title compound. NMR (CDCB): 2.90 (3H, s), 3.41 (3H, s), 3.84-3.87 (4H, m), 3.99-4.02 (4H, m), 5.29 (2H, br), 7.26 (IH, s), 7.53 (2H, d), 8.12 (2H, d), 9.30 (2H, s) MS (ESI+): MH+ 442.13 (10%), (MH+AcN) 483.2 (100%)

Reference： [1]Patent: WO2009/66084,2009,A1 .Location in patent: Page/Page column 93-94

12
[ 916587-44-5 ]
[ 58732-70-0 ]
[ 1062175-05-6 ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; water at 185℃; Microwave irradiation;

Reference： [1]Location in patent: experimental part Verheijen, Jeroen C.; Richard, David J.; Curran, Kevin; Kaplan, Joshua; Lefever, Mark; Nowak, Pawel; Malwitz, David J.; Brooijmans, Natasja; Toral-Barza, Lourdes; Zhang, Wei-Guo; Lucas, Judy; Hollander, Irwin; Ayral-Kaloustian, Semiramis; Mansour, Tarek S.; Yu, Ker; Zask, Arie [Journal of Medicinal Chemistry, 2009, vol. 52, # 24, p. 8010 - 8024]

13
[ 916587-44-5 ]
[ 5332-24-1 ]
[ 1246093-99-1 ]

Yield	Reaction Conditions	Operation in experiment
		Preparation of N-Methyl-4-(quinolin-3-yl)aniline (T477) 3-Bromoquinoline (42 mg, 0.2 mmol) and tert-butyl methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (66 mg, 0.2 mmol) were reacted using General Procedure (A) to afford tert-butyl methyl(4-(quinolin-3-yl)phenyl)carbamate a clear wax (44 mg, 66%). 1H NMR (400 MHz, CDCl3): δ 9.18 (d, J=2.4 Hz, 1H), 8.31 (d, J=2.0 Hz, 1H), 8.15 (m, 1H), 7.89 (m, 1H), 7.73 (m, 1H), 7.68 (m, 2H), 7.59 (m, 1H), 7.42 (m, 2H), 3.3 (s, 3H), 1.50 (s, 9H); MS (ESI): 335 (M+H+).

Reference： [1]Current Patent Assignee: ELI LILLY & CO - US2010/239496, 2010, A1

14
[ 916587-44-5 ]
[ 19493-45-9 ]
[ 1246094-00-7 ]

Yield	Reaction Conditions	Operation in experiment
18%		Preparation of 3-Chloroisoquinoline (33 mg, 0.2 mmol) and tert-butyl methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (66 mg, 0.2 mmol) were reacted using general procedure A to afford tert-butyl (4-(isoquinolin-3-yl)phenyl)(methyl)carbamate as a clear oil (12 mg, 18%). 1H NMR (400 MHz, CDCl3): delta 9.33 (s, 1H), 8.09 (m, 2H), 8.05 (s, 1H), 7.99 (m, 1H), 7.87 (m, 1H), 7.69 (m, 1H), 7.58 (m, 1H), 7.38 (m, 2H), 3.32 (s, 3H), 1.48 (s, 9H); MS (ESI): 335 (M+H+).

Reference： [1]Patent: US2010/239496,2010,A1

15
[ 916587-44-5 ]
[ 20146-63-8 ]
[ 1246093-98-0 ]

Yield	Reaction Conditions	Operation in experiment
68%		tert-Butyl methyl(4-(4-nitroquinolin-2-yl)phenyl)carbamate 2-Bromo-4-nitroquinoline (50 mg, 0.2 mmol) and tert-butyl methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (66 mg, 0.2 mmol) were reacted using General Procedure (A) to afford tert-butyl methyl(4-(4-nitroquinolin-2-yl)phenyl)carbamate as a yellow oil (52 mg, 68%). 1H NMR (400 MHz, CDCl3): δ 8.43-8.40 (m, 2H), 8.28 (m, 1H), 8.19 (m, 2H), 7.87 (m, 1H), 7.73 (m, 1H), 7.46 (m, 2H), 3.35 (s, 3H), 1.59 (s, 3H), 1.50 (s, 9H); MS (ESI): 380 (M+H+).
68%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 0.5h; Microwave irradiation;	tert-Butyl methyl(4-(4-nitroquinolin-2-yl)phenyl)carbamate General procedure: A mixture of aryl/heterocyclic halide (1.0 equiv.), boronic acid or boronate ester (1.1-1.5 equiv.), K2CO3 (3.0 equiv.) and Pd[PPh3]4 (0.01 -0.05 equiv) in DMF (30 mL) was irradiated in a Biotage Emrys Initiator microwave reactor (250 W) at 100 °C for 30 min. After cooling to room temperature, the solvent was removed in vacuo. The residue was purified on flash column chromatography over silica gel using EtOAc:Hexanes or EtOAc:DCM or MeOH:DCM as the eluent to afford the desired biaryl products. 2-Bromo-4-nitroquinoline (50 mg, 0.2 mmol) and tert-butyl methyl(4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)carbamate (66 mg, 0.2 mmol) were reacted using General Procedure (A) to afford tert-butyl methyl(4-(4-nitroquinolin-2-yl)phenyl)carbamate as a yellow oil (52 mg, 68%).

Reference： [1]Current Patent Assignee: ELI LILLY & CO - US2010/239496, 2010, A1
[2]Current Patent Assignee: ELI LILLY & CO - CN102985411, 2016, B Location in patent: Paragraph 0333-0336; 0461; 0462; 0464

16
[ 916587-44-5 ]
[ 1235382-38-3 ]
[ 1248555-83-0 ]

Yield	Reaction Conditions	Operation in experiment
75%	With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 1h; Inert atmosphere;	8a (8a) 2-(Trimethylsilyl)ethyl 4-{4-[(tert-butoxycarbonyl) (methyl)amino]phenyl}isoquinoline-6-carboxylate Into N,N-dimethylformamide (30 mL), 2-(trimethylsilyl)ethyl 4-[(trifluoromethyl)sulfonyl]oxy}isoquinoline-6-carboxylate (1.50 g, 3.56 mmol), potassium carbonate (2.46 g, 17.8 mmol), tert-butyl methyl--[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate (1.78 g, 5.34 mmol), and a [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium-dichloromethane complex (291 mg, 0.356 mmol) were dissolved, followed by stirring at 90°C for one hour under a nitrogen atmosphere. After cooling, the resulting reaction liquid was concentrated under reduced pressure and a solid was filtered off, followed by washing with dichloromethane. The resulting organic layer was concentrated under reduced pressure again. The residue thus obtained was purified by basic silica gel column chromatography (hexane : ethyl acetate, 100 : 0 - 80 : 20, V/V) and by neutral silica gel column chromatography (hexane : ethyl acetate, 100 : 0 - 50 : 50, V/V) to give the desired title compound (1.28 g, yield 75%). 1H-NMR (CDCl3) δ: 0.04 (9H, s), 1.09-1.13 (2H, m), 1.50 (9H, s), 3.35 (3H, s), 4.41-4.46 (2H, m), 7.42 (2H, d, J = 8.6 Hz), 7.47 (2H, d, J = 8.6 Hz), 8.08 (1H, d, J = 8.5 Hz), 8.20 (1H, d, J = 8.5 Hz), 8.54 (1H, s), 8.66 (1H, s), 9.29 (1H, s).

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - EP2418203, 2012, A1 Location in patent: Page/Page column 23

17
[ 916587-44-5 ]
[ 1248553-88-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: potassium carbonate / dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂ / N,N-dimethyl-formamide / 1 h / 90 °C / Inert atmosphere 2.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 2 h / Inert atmosphere 2.2: 4 h / 20 °C / Inert atmosphere 3.1: trifluoroacetic acid / dichloromethane / 3 h / 0 - 20 °C 3.2: 0 °C 4.1: acetic acid / 4 h / 0 - 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - EP2418203, 2012, A1

18
[ 916587-44-5 ]
[ 1248555-85-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: potassium carbonate / dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂ / N,N-dimethyl-formamide / 1 h / 90 °C / Inert atmosphere 2.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 2 h / Inert atmosphere 2.2: 4 h / 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - EP2418203, 2012, A1

19
[ 916587-44-5 ]
[ 1248555-87-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: potassium carbonate / dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂ / N,N-dimethyl-formamide / 1 h / 90 °C / Inert atmosphere 2.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 2 h / Inert atmosphere 2.2: 4 h / 20 °C / Inert atmosphere 3.1: trifluoroacetic acid / dichloromethane / 3 h / 0 - 20 °C 3.2: 0 °C

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - EP2418203, 2012, A1

20
[ 330793-01-6 ]
[ 74-88-4 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
70%	With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 18h;	2.1 Example 2 N-hydroxy-N'-methyl-2-('-(methylamino)biphenyl-4-yl]carbonyl}amino)propanediamide (Compound 2) (1) 60% Sodium hydride (0.55 g) and methyl iodide (1.2 mL) were added to a DMF (6.0 mL) solution of t-butyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (2.0 g), and the mixture was stirred for 18 hours at room temperature. Ethyl acetate and water were added to the reaction mixture, and the organic layer was isolated. The extract was washed sequentially with water and brine, and dried over anhydrous sodium sulfate. Then, the desiccant was filtered out, whereafter the solvent was distilled off under reduced pressure. Hexane was added to the residue, and the precipitated solid was collected by filtration to obtain t-butyl=methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (white solid) (1.46 g, 70%).1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.34 (12H, s), 1.45 (9H, s), 3.27 (3H, s), 7.24 (2H, d, J=8.4 Hz), 7.76 (2H, d, J=8.4 Hz)
	Stage #1: (4-tert-butoxycarbonylaminophenyl)boronic acid pinacol ester With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.333333h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran; mineral oil at 0 - 20℃;	Intermediate 18terf-butyl methyl (4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- mate[0102] Under N2, to a solution of terf-butyl 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan- 2-yl)phenylcarbamate (500 mg, 1 .57 mmol) in anhydrous THF(4 ml_), was slowly added sodium hydride (94 mg, 2.35 mmol) at 0 °C. The mixture was stirred at room temperature for 20 minutes, then cooled to 0 °C. CH3I (445 mg, 3.13 mmol) was slowly added. After the completion of the addition, the reaction mixture was stirred at room temperature overnight, quenched with H2O, and extracted with EtOAc. The combined extracts were concentrated, and the residue was purified by flash chromatography to give the title compound. MS (m/z): 278 (M-56)+.
	Stage #1: (4-tert-butoxycarbonylaminophenyl)boronic acid pinacol ester With sodium hydride In tetrahydrofuran at 0 - 20℃; for 0.333333h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	18 tert-butyl methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate Under N2, to a solution of tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate (500 mg, 1.57 mmol) in anhydrous THF (4 mL), was slowly added sodium hydride (94 mg, 2.35 mmol) at 0° C. The mixture was stirred at room temperature for 20 minutes, then cooled to 0° C. CH3I (445 mg, 3.13 mmol) was slowly added. After the completion of the addition, the reaction mixture was stirred at room temperature overnight, quenched with H2O, and extracted with EtOAc. The combined extracts were concentrated, and the residue was purified by flash chromatography to give the title compound. MS (m/z): 278 (M-56)+.

Reference： [1]Current Patent Assignee: TAISHO PHARMACEUTICAL HOLDINGS CO., LTD.; FUJIFILM HOLDINGS CORP. - EP2562155, 2013, A1 Location in patent: Paragraph 0222-0223
[2]Current Patent Assignee: HUTCHISON CHINA MEDITECH LTD. - WO2012/167423, 2012, A1 Location in patent: Page/Page column 38
[3]Current Patent Assignee: HUTCHISON CHINA MEDITECH LTD. - US2014/121200, 2014, A1 Location in patent: Paragraph 0181; 0182

21
[ 916587-44-5 ]
[ 1344700-19-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; potassium phosphate / water; N,N-dimethyl-formamide / 3.5 h / 90 °C / Inert atmosphere 2: HATU; N-ethyl-N,N-diisopropylamine / N,N-dimethyl-formamide / 16 h / 20 °C

Reference： [1]Current Patent Assignee: TAISHO PHARMACEUTICAL HOLDINGS CO., LTD.; FUJIFILM HOLDINGS CORP. - EP2562155, 2013, A1

22
[ 916587-44-5 ]
[ 1344693-12-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: bis-triphenylphosphine-palladium(II) chloride; triphenylphosphine; potassium phosphate / water; N,N-dimethyl-formamide / 3.5 h / 90 °C / Inert atmosphere 2.1: HATU; N-ethyl-N,N-diisopropylamine / N,N-dimethyl-formamide / 16 h / 20 °C 3.1: trifluoroacetic acid; methoxybenzene / 1 h / 20 °C 3.2: 1 h / 20 °C

Reference： [1]Current Patent Assignee: TAISHO PHARMACEUTICAL HOLDINGS CO., LTD.; FUJIFILM HOLDINGS CORP. - EP2562155, 2013, A1

23
[ 916587-44-5 ]
[ 619-58-9 ]
[ 1344700-18-0 ]

Yield	Reaction Conditions	Operation in experiment
71%	With bis-triphenylphosphine-palladium(II) chloride; potassium phosphate; triphenylphosphine In water; N,N-dimethyl-formamide at 90℃; for 3.5h; Inert atmosphere;	2.2 N-hydroxy-N'-methyl-2-('-(methylamino)biphenyl-4-yl]carbonyl}amino)propanediamide (Compound 2) (2) PdCl2(PPh3)2 (119 mg), triphenylphosphine (89 mg), potassium phosphate (1.44 g) and water (1.7 mL) were added to a DMF (17 mL) solution of t-butyl=methyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (846 mg), as obtained in Example 2-(1), and 4-iodobenzoic acid (420 mg), and the mixture was stirred in a nitrogen atmosphere for 3.5 hours at 90°C. After the reaction mixture was allowed to cool, ethyl acetate and water were added, and the mixture was adjusted to pH 3 with 1 mol/L of hydrochloric acid. The organic layer was isolated, and the extract was washed sequentially with water and brine. The system was dried over anhydrous magnesium sulfate and, after addition of silica gel (10.0 g), the mixture was stirred for 15 minutes at room temperature. The desiccant and the silica gel were filtered out, and then the solvent was distilled off under reduced pressure. Hexane was added to the residue, and the precipitated solid was collected by filtration, and washed with an IPE/hexane=1/1 solvent mixture. IPE was added to the resulting solid, and the mixture was stirred for 15 minutes at room temperature. Then, the remaining solid was collected by filtration to obtain 4'-((t-butoxycarbonyl)(methyl)amino)biphenyl-4-carboxylic acid (light brown solid) (396 mg, 71%). 1 H NMR (400 MHz, DMSO-d6) δ ppm 1.42 (9H, s), 3.23 (3H, s), 7.41 (2H, d, J=8.5 Hz), 7.72 (2H, d, J=8.5 Hz), 7.80 (2H, d, J=8.3 Hz), 8.01 (2H, d, J=8.3 Hz), 12.80 - 13.14 (1H, br. s.)

Reference： [1]Current Patent Assignee: TAISHO PHARMACEUTICAL HOLDINGS CO., LTD.; FUJIFILM HOLDINGS CORP. - EP2562155, 2013, A1 Location in patent: Paragraph 0224

24
[ 916587-44-5 ]
[ 1374108-41-4 ]
[ 1374108-67-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; water at 90℃; for 1.5h; Inert atmosphere;	1 Synthesis of 67 Synthesis of 67 To a mixture of 34 (1.50 g, 3.3 mmol), 66 (1.2 g, 3.6 mmol) and 1,2-dimethoxyethane (15 ml), an aqueous 2M sodium carbonate solution (3.3 ml, 6.6 mmol) and tetrakistriphenylphosphine palladium (189 mg, 0.16 mmol) were added under an argon atmosphere, and the mixture was stirred at 90°C for 1.5 hours. The reaction solution was allowed to return to room temperature and insolubles were removed by filtration, and the solution was washed with chloroform. The filtrate and the wash were combined and the mixture was washed with an aqueous saturated sodium hydrogen carbonate solution and dried, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel flash column chromatography (eluting solvent: ethyl acetate/n-hexane = 1/9, 1/4, 1/2) to obtain 67 (1.70 g, 100%) as a colorless oily substance. APCI-MS m/z 517[M+H]+

Reference： [1]Current Patent Assignee: GENERAL ELECTRIC CO - EP2634177, 2013, A1 Location in patent: Paragraph 0237; 0238

25
[ 916587-44-5 ]
[ 1374108-60-7 ]
[ 1374109-01-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 8h; Inert atmosphere;	1 Synthesis of 121 Synthesis of 121 To a 1,2-dimethoxyethane (65 ml) solution of 59 (2.01 g, 7.99 mmol) and 66 (2.66 g, 7.99 mmol), potassium carbonate (3.31 g, 24.0 mmol), water (1.39 ml) and tetrakistriphenylphosphine palladium (920 mg, 0.80 mmol) were added under an argon atmosphere, and the mixture was stirred at 80°C for 8 hours. The reaction solution was allowed to return to room temperature and water was added, and the solution was extracted with ethyl acetate. The extraction liquid was washed with water and dried, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluting solvent: ethyl acetate/n-hexane = 1/19, 1/9, 1/4) to obtain 121 (3.38 g, 100%) as a pale yellow oily substance. APCI-MS m/z 423[M+H]+

Reference： [1]Current Patent Assignee: GENERAL ELECTRIC CO - EP2634177, 2013, A1 Location in patent: Paragraph 0319; 0320

26
[ 916587-44-5 ]
[ 1374108-70-9 ]
[ 1374108-86-7 ]

Yield	Reaction Conditions	Operation in experiment
100%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 16h; Inert atmosphere;	1 Synthesis of 103 Synthesis of 103 To a 1,2-dimethoxyethane (38 ml) solution of 70 (2.02 g, 4.66 mmol) and 66 (1.55 g, 4.66 mmol), potassium carbonate (1.93 g, 13.97 mmol), water (0.81 ml) and tetrakistriphenylphosphine palladium (540 mg, 0.47 mmol) were added under an argon atmosphere, and the mixture was stirred at 80°C for 16 hours. The reaction solution was allowed to return to room temperature and water was added, and the solution was extracted with ethyl acetate. The extraction liquid was washed with water and dried, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluting solvent: ethyl acetate/n-hexane = 1/4) to obtain 103 (2.82 g, 100%) as a pale pink oily substance. APCI-MS m/z 605[M+H]+

Reference： [1]Current Patent Assignee: GENERAL ELECTRIC CO - EP2634177, 2013, A1 Location in patent: Paragraph 0290; 0291

27
[ 916587-44-5 ]
[ 1374108-96-9 ]
[ 1374109-11-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,2-dimethoxyethane; water at 85℃; for 16h; Inert atmosphere;	1 Synthesis of 132 Synthesis of 132 A mixture of 115 (625 mg, 1.69mmol), 66 (619 mg, 1.86mmol), potassium carbonate (467 mg, 3.4 mmol), tetrakistriphenylphosphine palladium (195 mg, 0.169mmol) and 1,2-dimethoxyethane (4.5ml)-water (0.5 ml) was stirred under an argon atmosphere at 85°C for 16 hours. The reaction solution was allowed to return to room temperature and water was added, and the solution was extracted with ethyl acetate. The extraction liquid was dried and the solvent was distilled off under reduced pressure, and then the residue was purified by silica gel flash column chromatography (eluting solvent: n-hexane, ethyl acetate/n-hexane = 1/19, 1/9, 1/6) to obtain 132 (920 mg, 100%) as a colorless oily substance. APCI-MS m/z 541[M+H]+

Reference： [1]Current Patent Assignee: GENERAL ELECTRIC CO - EP2634177, 2013, A1 Location in patent: Paragraph 0339; 0340

28
[ 916587-44-5 ]
[ 1374108-98-1 ]
[ 1374108-99-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,2-dimethoxyethane; water at 85℃; for 6h; Inert atmosphere;	1 Synthesis of 119 Synthesis of 119 A mixture of 118 (1.83 g, 4.9 mmol), 66 (1.73 g, 5.2 mmol), potassium carbonate (1.37 g, 9.9 mmol), tetrakistriphenylphosphine palladium (300 mg, 0.26 mmol) and 1,2-dimethoxyethane (45 ml)-water (5 ml) was stirred under an argon atmosphere at 85°C for 2 hours and tetrakistriphenylphosphine palladium (283 mg, 0.245 mmol) and potassium carbonate (678 mg, 4.9 mmol) were added, followed by stirring at the same temperature for 4 hours. The reaction solution was allowed to return to room temperature and water was added, and the solution was extracted with ethyl acetate. The extraction liquid was dried and the solvent was distilled off under reduced pressure and then the residue was purified by silica gel flash column chromatography (eluting solvent: n-hexane, ethyl acetate/n-hexane = 1/9) to obtain 119 (2.28 g, 85%) as a pale yellow oily substance. APCI-MS m/z 541[M+H]+

Reference： [1]Current Patent Assignee: GENERAL ELECTRIC CO - EP2634177, 2013, A1 Location in patent: Paragraph 0312; 0314

29
[ 916587-44-5 ]
3-(6-bromoimidazo[1,2-a]pyrimidin-2-yl)-4-chloroaniline [ No CAS ]
tert-butyl (4-(2-(5-amino-2-chlorophenyl)imidazo[1,2-a]pyrimidin-6-yl)phenyl)(methyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,4-dioxane; water at 120℃; for 0.5h; Inert atmosphere; Sealed tube; Microwave irradiation;	5 Synthesis of tert-butyl (4-(2-(5-amino-2-chlorophenyl)imidazo[1,2-a]pyrimidin-6-yl)phenyl)(methyl)carbamate (I-11) General procedure: Example 5 Synthesis of tert-butyl (4-(2-(5-amino-2-chlorophenyl)imidazo[1,2-a]pyrimidin-6-yl)phenyl)(methyl)carbamate (I-11) In a 10 ml microwave via I-4 (140 mg, 0.48 mmol, 1.0 eq.), boronic ester (216 mg, 0.65 mmol, 1.5 eq.), Tetrakis(triphenylphosphine)palladium(0(30 mg, 0.02 mmol, 0.05 eq.) and 1 M sodium carbonate solution (0.87 ml, 0.87 mM, 2.0 eq.) were added. The vial was sealed and purged with nitrogen. 1,4-dioxane was added into the vial via a syringe and the solution was microwaved for 30 minutes at 120° C. The reaction mixture was added ethyl acetate and filtered. Silica gel was added and evaporated dry. Purification was done by ISCO, 25% ethyl acetate in hexane isocratically, then via a slow gradient through to 80% ethyl acetate. The system was held at 80% to separate the target compound I-11. m/z (ESI): 451 (M+H+), 1H NMR (600 MHz, DMSO-D6) δ 9.35 (d, J=2.6, 1H), 8.94 (d, J=2.6, 1H), 8.50 (s, 1H), 7.75 (d, J=8.7, 2H), 7.58 (d, J=2.9, 1H), 7.46 (d, J=8.7, 2H), 7.17 (d, J=8.5, 1H), 6.58 (m, 1H), 5.41 (s, 2H), 3.24 (s, 3H), 1.43 (s, 9H).

Reference： [1]Current Patent Assignee: NOVARTIS AG; Novartis (w/o Sandoz) - US2014/275119, 2014, A1 Location in patent: Paragraph 0429

30
[ 916587-44-5 ]
2-(6-bromobenzo[d]thiazol-2-yl)-N-(2-(cyclopropylamino)-2-oxoethyl)-2-((2-methoxyethyl)sulfonyl)acetamide [ No CAS ]
tert-butyl N-{4-[2-([(cyclopropylcarbamoyl)methyl]carbamoyl}(2-methoxyethanesulfonyl)methyl)-1,3-benzothiazol-6-yl]phenyl}-N-methylcarbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
37%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,4-dioxane at 100℃; for 1h; Inert atmosphere;	60 General procedure: Compound ic (100 mg, 0.26 mmol), and (4- (((benzyloxy)carbonyl)amino)phenyl)boronic acid (88 mg, 0.32 mmol) in dioxane (4 mL)/2M Na2CO3 (2 mL) was purged with argon and heated at 100 °C for 1 h. The reaction mixture was filtered through CELITE, concentrated under reduced pressure andpurified using reverse phase HPLC (PHENOMENEX Luna Axia 5 t C18, 21.2x100, UV at 220 nm, 10 to 70% B over 30 mm with 10 mm hold time, solvent A: 90% water/ACN/0. 1%TFA, solvent B:90% ACN/water/0. 1%TFA, Flow rate 20 mL/min; detector at 254) to isolate Compound id (84 mg, 61% yield) as an off-white solid. Example 60 (6.9 mg, 37% yield) was prepared from Compound 60b as described in the general procedure given for Compound id. HPLC RT = 1.91 mm (LCMS Method N). MS(ES): m/z = 617.2 [M+H]. ‘H NMR (500MHz, DMSO-d6) ö 8.99 (s, 1H), 8.48 (d, J=1.9 Hz, 1H), 8.15 (d, J=8.5 Hz, 1H), 8.02 (d, J=4.1 Hz, 1H), 7.87 (dd, J=8.5, 1.9 Hz, 1H), 7.79 - 7.70 (m, 2H), 7.47 - 7.39 (m, J=8.5 Hz, 2H), 6.20 (s, 1H),3.85 - 3.68 (m, 6H), 3.28 (s, 3H), 3.26 - 3.21 (m, 3H), 2.64 (d, J=3.9 Hz, 1H), 1.47 - 1.38 (m, 9H), 0.69 - 0.57 (m, 2H), 0.46 - 0.36 (m, 2H). EL IC50 = 3 nM.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2015/105749, 2015, A1 Location in patent: Paragraph 00176; 00188

31
tert-butyl (4-fluorophenyl)(methyl)carbamate [ No CAS ]
[ 73183-34-3 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
51.6%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; copper(l) iodide; cesium fluoride; tricyclohexylphosphine In toluene at 80℃; for 24h; Inert atmosphere;

Reference： [1]Niwa, Takashi; Ochiai, Hidenori; Watanabe, Yasuyoshi; Hosoya, Takamitsu [Journal of the American Chemical Society, 2015, vol. 137, # 45, p. 14313 - 14318]

32
[ 60144-53-8 ]
[ 916587-44-5 ]

Reference： [1]Journal of the American Chemical Society,2015,vol. 137,p. 14313 - 14318

33
[ 104-96-1 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: <i>tert</i>-butyl alcohol / 24 h / 40 °C / Inert atmosphere 2.1: sodium hydride / N,N-dimethyl-formamide; tetrahydrofuran; mineral oil / 0.5 h / 0 °C / Inert atmosphere 2.2: 12 h / 0 - 20 °C / Inert atmosphere 3.1: tricyclohexylphosphine; [Rh(OH)(cod)]2 / hexane / 1 h / 80 °C / Glovebox; Inert atmosphere 3.2: 12 h / 80 °C / Glovebox; Inert atmosphere

Reference： [1]Uetake, Yuta; Niwa, Takashi; Hosoya, Takamitsu [Organic Letters, 2016, vol. 18, # 11, p. 2758 - 2761]

34
tert-butyl N-methyl-N-(4-(methylthio)phenyl)carbamate [ No CAS ]
[ 73183-34-3 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
86.7%	Stage #1: bis(pinacol)diborane With [Rh(OH)(cod)]2; tricyclohexylphosphine In hexane at 80℃; for 1h; Glovebox; Inert atmosphere; Stage #2: tert-butyl N-methyl-N-(4-(methylthio)phenyl)carbamate In hexane at 80℃; for 12h; Glovebox; Inert atmosphere;

Reference： [1]Uetake, Yuta; Niwa, Takashi; Hosoya, Takamitsu [Organic Letters, 2016, vol. 18, # 11, p. 2758 - 2761]

35
[ 916587-44-5 ]
[ 42101-92-8 ]
tert-butyl methyl(4-(naphthalen-2-ylmethyl)phenyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; cesium fluoride; 1,3-dicyclohexyl-1H-imidazol-3-ium chloride; sodium t-butanolate In toluene at 120℃; for 12h; Glovebox; Inert atmosphere; Sealed tube;

Reference： [1]Tobisu, Mamoru; Yasutome, Ayaka; Kinuta, Hirotaka; Nakamura, Keisuke; Chatani, Naoto [Organic Letters, 2014, vol. 16, # 21, p. 5572 - 5575]

36
[ 916587-44-5 ]
C₁₅H₁₆ClNO₃ [ No CAS ]
C₂₇H₃₂N₂O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 90℃;

Reference： [1]Current Patent Assignee: CLINO - US2016/244411, 2016, A1 Location in patent: Paragraph 0299

37
phenyl 4-((tert-butoxycarbonyl)(methyl)amino)benzoate [ No CAS ]
[ 73183-34-3 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
61%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; tributylphosphine; lithium carbonate In 1,4-dioxane at 160℃; for 36h; Glovebox; Sealed tube;

Reference： [1]Guo, Lin; Rueping, Magnus [Chemistry - A European Journal, 2016, vol. 22, # 47, p. 16787 - 16790]

38
[ 662112-08-5 ]
[ 24424-99-5 ]
[ 916587-44-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: dmap / acetonitrile / 12 h / 20 °C / Inert atmosphere 2: bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; tributylphosphine; lithium carbonate / 1,4-dioxane / 36 h / 160 °C / Glovebox; Sealed tube

Reference： [1]Guo, Lin; Rueping, Magnus [Chemistry - A European Journal, 2016, vol. 22, # 47, p. 16787 - 16790]

39
[ 916587-44-5 ]
α-cumyl bromodifluoromethanesulfenate [ No CAS ]
tert-butyl (4-((bromodifluoromethyl)thio)phenyl)(methyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With [(1,2-bis(diphenylphosphino)ethane)CuCl]; sodium t-butanolate In toluene at 50℃; for 2h; Glovebox; Sealed tube;	25 In the glove box, the DPPECuCl (25 mg, 10 µM %) and NaOt Bu (15 mg, 30 µM %) is added to the in tube sealing, then tert-butyl (4-phenylboric acid pinacol ester)(methyl)carbamate (0.5 mmol, 1.0 equiv, 166 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 181 mg, yield 98%. After hydrogen spectrum identifying the purity of greater than 95%.
181 mg	With [(1,2-bis(diphenylphosphino)ethane)CuCl]; sodium t-butanolate In toluene at 50℃; for 2h; Inert atmosphere; Schlenk technique;

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN107011219, 2017, A Location in patent: Paragraph 0112-0114
[2]Wu, Jiang; Zhao, Qunchao; Wilson, Thomas C.; Verhoog, Stefan; Lu, Long; Gouverneur, Véronique; Shen, Qilong [Angewandte Chemie - International Edition, 2019, vol. 58, # 8, p. 2413 - 2417][Angew. Chem., 2019, vol. 131, # 8, p. 2435 - 2439,5]

40
[ 916587-44-5 ]
C₁₈H₁₅BN₂ [ No CAS ]
C₃₀H₃₀BN₃O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	With oxygen; palladium diacetate; sodium carbonate In N,N-dimethyl-formamide at 50℃; for 5h;	7.2 (2) Synthesis of 4-N-BOC-N-methyl-4'-boronostilbene-DAN protected type (41) N-BOC-N-methyl-4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (MW=333.21, Wako322-52381)Was weighed 397 mg (1.2 mmol),36 mg of palladium acetate was added as a palladium catalyst,213 mg (2 mmol) of sodium carbonate was added as a base.Dissolve them in 5 mL DMF,In addition to compound 40,50°C under oxygen environment,React for 5 hours with stirring,Compound 41 was obtained (yield 40%, TLC evaluation).

Reference： [1]Current Patent Assignee: CANCER INTELLIGENCE CARE SYS - JP2020/66619, 2020, A Location in patent: Paragraph 0123; 0124

41
[ 916587-44-5 ]
[ 3038-48-0 ]
C₂₁H₂₂F₃NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With (2S,3S)-N-acetyl-2-amino-3-methylpentanoic acid; 2,5-di-tert-butyl-p-benzoquinone; oxygen; potassium hydrogencarbonate In tert-Amyl alcohol at 90℃; for 24h;

Reference： [1]Salazar, Chase A.; Flesch, Kaylin N.; Haines, Brandon E.; Zhou, Philip S.; Musaev, Djamaladdin G.; Stahl, Shannon S. [Science, 2020, vol. 370, # 6523, p. 1454 - 1460]

42
[ 916587-44-5 ]
[ 1577233-12-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: tetrahydrofuran / 0.02 h / 20 °C / Sealed tube 2: N,N,N,N,-tetramethylethylenediamine; iron(II) chloride; magnesium bromide / tetrahydrofuran / 2 h / 50 °C / Sealed tube; Glovebox; Inert atmosphere

Reference： [1]Hu, Jinbo; Miao, Wenjun; Ni, Chuanfa; Wei, Zhiqiang [Angewandte Chemie - International Edition, 2021, vol. 60, # 24, p. 13597 - 13602][Angew. Chem., 2021, vol. 133, p. 13709 - 13714,6]

43
[ 916587-44-5 ]
[ 598-30-1 ]
C₂₂H₃₇BNO₄^(1-)*Li⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran at 20℃; for 0.0166667h; Sealed tube;

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Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
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. 916587-44-5 ] {[proInfo.proName]}

Quality Control of [ 916587-44-5 ]

Related Doc. of [ 916587-44-5 ]

Product Details of [ 916587-44-5 ]

Safety of [ 916587-44-5 ]

Application In Synthesis of [ 916587-44-5 ]

[ 916587-44-5 ] Synthesis Path-Downstream 1~43

Related Functional Groups of [ 916587-44-5 ]

Organoboron

Aryls

Amides

Esters

Amines

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 916587-44-5 ]