[ CAS No. 3034-55-7 ]

Name: 3034-55-7|5-Bromothiazole|97%
Brand: Ambeed
SKU: A145518
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Quality Control of [ 3034-55-7 ]

COA NMR CNMR HPLC LC-MS

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Product Details of [ 3034-55-7 ]

CAS No. :	3034-55-7	MDL No. :	MFCD07787394
Formula :	C₃H₂BrNS	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	DWUPYMSVAPQXMS-UHFFFAOYSA-N
M.W :	164.02	Pubchem ID :	546059
Synonyms :

Calculated chemistry of [ 3034-55-7 ]

Physicochemical Properties

Num. heavy atoms :	6
Num. arom. heavy atoms :	5
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	29.81
TPSA :	41.13 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.89 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.54
Log Po/w (XLOGP3) :	1.98
Log Po/w (WLOGP) :	1.91
Log Po/w (MLOGP) :	0.53
Log Po/w (SILICOS-IT) :	3.07
Consensus Log Po/w :	1.81

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.72
Solubility :	0.312 mg/ml ; 0.0019 mol/l
Class :	Soluble
Log S (Ali) :	-2.47
Solubility :	0.556 mg/ml ; 0.00339 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.14
Solubility :	1.2 mg/ml ; 0.00729 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.27

Safety of [ 3034-55-7 ]

Signal Word:	Danger	Class:	8
Precautionary Statements:	P261-P264-P280-P301+P312-P302+P352-P305+P351+P338	UN#:	1760
Hazard Statements:	H302-H315-H317-H318-H335	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 3034-55-7 ]

* 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 [ 3034-55-7 ]
Downstream synthetic route of [ 3034-55-7 ]

[ 3034-55-7 ] Synthesis Path-Upstream 1~8

1
[ 3034-22-8 ]
[ 3034-55-7 ]

Reference： [1] Journal of Organic Chemistry, 2017, vol. 82, # 11, p. 5947 - 5951
[2] Bulletin de la Societe Chimique de France, 1962, p. 2075 - 2078
[3] Patent: WO2008/57336, 2008, A2, . Location in patent: Page/Page column 40-41

2
[ 4175-78-4 ]
[ 3034-55-7 ]

Reference： [1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1986, vol. 22, # 6, p. 663 - 666[2] Khimiya Geterotsiklicheskikh Soedinenii, 1986, vol. 22, # 6, p. 837 - 840
[3] Journal of Organic Chemistry, 2006, vol. 71, # 10, p. 3754 - 3761

3
[ 288-47-1 ]
[ 3034-55-7 ]

Reference： [1] Oriental Journal of Chemistry, 2015, vol. 31, # 4, p. 2239 - 2245
[2] Oriental Journal of Chemistry, 2015, vol. 31, # 4, p. 2239 - 2245

4
[ 79265-30-8 ]
[ 3034-55-7 ]
[ 108306-64-5 ]

Reference： [1] Synthesis, 1986, # 9, p. 757 - 760

5
[ 3034-55-7 ]
[ 141-78-6 ]
[ 24295-03-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: With n-butyllithium In diethyl ether; hexane at -78℃; for 0.833333 h; Stage #2: at -78 - 20℃; for 0.533333 - 0.55 h;	To cooled (-78 °C) diethyl ether (30ml) was added n-butyllithium (13.2 ml of 2.5M solution in hexanes), followed by the dropwise addition of a solution of 2- bromothiazole (2. 7ml) in diethyl ether (35ml) over 20 minutes. The resulting mixture was stirred for 30 minutes AT-78 °C. Under rapid stirring, ethylacetate (5ml) was added over 2-3 minutes. The mixture was stirred for 30 minutes AT-78 °C, then allowed to warm to ambient and quenched with saturated sodium bicarbonate solution (50ml). More diethyl ether (50ml) and water (50ml) was added. The organic phase was separated, washed with water and brine, dried with magnesium sulfate, filtered and concentrated. The residue was purified by flash chromatography (20percent ethyl acetate/petroleum ether) to afford the sub-title compound as a yellow oil (3.3g, 87percent) ; 1H NMR (4OOMHZ, CDC13) otilde; 2.7 (3H, s), 7.65 (1H, s), 8.0 (1H, s); MS (ES+) 128.1 (M+1).

Reference： [1] Patent: WO2004/87699, 2004, A2, . Location in patent: Page 82

6
[ 3034-55-7 ]
[ 14527-41-4 ]

Reference： [1] Recueil des Travaux Chimiques des Pays-Bas, 1954, vol. 73, p. 325,329

7
[ 3034-55-7 ]
[ 64-17-5 ]
[ 201230-82-2 ]
[ 32955-22-9 ]

Reference： [1] Tetrahedron Letters, 1984, vol. 25, # 51, p. 5939 - 5942

8
[ 3034-55-7 ]
[ 73183-34-3 ]
[ 1086111-09-2 ]

Reference： [1] Journal of Medicinal Chemistry, 2015, vol. 58, # 12, p. 5053 - 5074
[2] Patent: WO2009/151598, 2009, A1, . Location in patent: Page/Page column 167

[ 3034-55-7 ] Synthesis Path-Downstream 1~69

1
[ 3034-55-7 ]
[ 14527-41-4 ]

Reference： [1]Recueil des Travaux Chimiques des Pays-Bas,1954,vol. 73,p. 325,329

2
[ 3034-55-7 ]
[ 75-77-4 ]
[ 79265-36-4 ]

Reference： [1]Phosphorus and Sulfur and the Related Elements,1985,vol. 24,p. 1 - 38
[2]Journal of the Chemical Society. Chemical communications,1981,p. 655 - 656

3
[ 3034-55-7 ]
[ 696-63-9 ]
5-(4-Methoxy-phenylsulfanyl)-thiazole [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1984,vol. 114,p. 279 - 282

4
[ 3034-55-7 ]
[ 108-40-7 ]
5-m-Tolylsulfanyl-thiazole [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1984,vol. 114,p. 279 - 282

5
[ 3034-55-7 ]
[ 2037-31-2 ]
5-(3-Chloro-phenylsulfanyl)-thiazole [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1984,vol. 114,p. 279 - 282

7
[ 3034-55-7 ]
[ 930-69-8 ]
5-(phenylthio)thiazole [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1984,vol. 114,p. 279 - 282

8
[ 3034-55-7 ]
[ 140-29-4 ]
[ 130161-32-9 ]

Reference： [1]Heterocycles,1990,vol. 31,p. 1115 - 1127

9
[ 3034-55-7 ]
[ 109299-79-8 ]
[ 127236-14-0 ]

Reference： [1]Journal of Heterocyclic Chemistry,1990,vol. 27,p. 2165 - 2173

10
[ 3034-55-7 ]
[ 108306-58-7 ]
[ 111185-06-9 ]

Reference： [1]Synthesis,1987,p. 185 - 186

11
[ 3034-55-7 ]
[ 108306-59-8 ]
[ 19960-72-6 ]

Reference： [1]Synthesis,1987,p. 185 - 186

12
[ 3034-55-7 ]
[ 108-98-5 ]
5-(phenylthio)thiazole [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1984,vol. 114,p. 279 - 282

13
[ 3034-55-7 ]
[ 106-45-6 ]
5-p-Tolylsulfanyl-thiazole [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1984,vol. 114,p. 279 - 282

14
[ 3034-55-7 ]
[ 201230-82-2 ]
[ 67-63-0 ]
[ 111160-48-6 ]
[ 101128-45-4 ]

Reference： [1]Journal of Organic Chemistry,1987,vol. 52,p. 5733 - 5740

15
[ 3034-55-7 ]
[ 7605-28-9 ]
[ 143031-95-2 ]

Reference： [1]Synthesis,1992,p. 552 - 554

17
[ 4175-78-4 ]
[ 3034-55-7 ]

Reference： [1]Chemistry of Heterocyclic Compounds,1986,vol. 22,p. 663 - 666
Khimiya Geterotsiklicheskikh Soedinenii,1986,vol. 22,p. 837 - 840
[2]Journal of Organic Chemistry,2006,vol. 71,p. 3754 - 3761

19
[ 3034-55-7 ]
[ 14347-78-5 ]
[ 143145-71-5 ]

Reference： [1]Journal of Organic Chemistry,1992,vol. 57,p. 5158 - 5162

20
[ 3034-55-7 ]
[ 19960-72-6 ]

Reference： [1]Journal of Materials Chemistry A,2019,vol. 7,p. 14153 - 14162
[2]Acta Crystallographica, Section C: Crystal Structure Communications,1995,vol. 51,p. 76 - 77

21
[ 3034-52-4 ]
[ 3034-55-7 ]
2-chloro-5,5'-bithiazole [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2006,vol. 71,p. 3754 - 3761

22
[ 887615-93-2 ]
[ 3034-55-7 ]
[ 887615-95-4 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 2535 - 2538

23
[ 3034-55-7 ]
(5-chlorothiophen-2-yl)boronic acid [ No CAS ]
[ 935458-27-8 ]

Reference： [1]Journal of Medicinal Chemistry,2007,vol. 50,p. 1546 - 1557

24
[ 3034-55-7 ]
[ 109-81-9 ]
N₁-methyl-N₁-(thiazol-5-yl)ethane-1,2-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
6%	With copper; copper(l) chloride; In isopropyl alcohol; at 70℃; for 1h;	a) Synthesis of N1-methyl-N1-(thiazol-5-yl)ethane-1,2-diamine 37 mg (0.6 mmol) copper and 172 mg (1.7 mmol) copper(I) chloride were added to a solution of 1.15 ml (10.5 mmol) <strong>[3034-55-7]5-bromothiazol</strong> and 5.6 ml (63.0 mmol) N-methyl-ethylene-diamine in isopropanol (6 ml). Heating was subsequently performed for 1 h to 70 C. Concentration was subsequently performed in a vacuum. The residue was received with brine (40 ml) and DCM (20 ml) and the phases were separated. The organic phase was dried over MgSO4, filtered and concentrated in a vacuum. CC (DCE/EtOH/conc. NH4OH 5:1:0.06) was performed with the residue, whereby 104 mg (0.7 mmol, 6%) N1-methyl-N1-(thiazol-5-yl)ethane-1,2-diamine was obtained.

Reference： [1]Patent: US2008/261996,2008,A1 .Location in patent: Page/Page column 45

25
[ 3034-55-7 ]
[ 1461-22-9 ]
[ 157025-33-7 ]

Yield	Reaction Conditions	Operation in experiment
31%		To a stirring solution of <strong>[3034-55-7]2-bromothiazole</strong> 33 (5 g, 30.48 mmol) in diethyl ether (35 mL) under inert atmosphere was added -butyl lithium (12.2 mL, 33.53 mmol, 2.5 M solution in hexane) at -70 C and stirred for 30 min. To this was added a solution of tributyltin chloride (10 mL, 30.48 mmol) in diethyl ether (15 mL) dropwise for 10 min at -70 C and stirred at the same temperature for 4 h; warmed to RT and stirred for 2 h. The reaction was monitored by TLC; after completion of the reaction, the reaction mixture was diluted with water (100 mL) and extracted with diethylether (3 x 50 mL) and washed with saturated potassium fluoride solution (50 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo to obtain the crude. The crude was purified through column chromatography using 25- 30% EtOAc/ hexanes to afford compound 37 (3.5 g, 31%) as white solid. TLC: 30% EtOAc/ hexanes (Rf. 0.4); 1H NMR (DMSO-i/i, 400 MHz): delta 9.35 (s, IH), 7.89 (s, IH), 1.58-1.47 (m, 6H), 1.34-1.24 (m, 6H), 1.13 (t, J= 8.0 Hz, 6H), 0.85 (t, J= 7.3 Hz, 9H).
		5-Tributylstannylthiazole; [Show Image] A hexane solution of n-BuLi (4.14 mL, 10 mmol) was added dropwise to an anhydrous tetrahydrofuran solution of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (0.46 mL, 5.0 mmol) at -78C under nitrogen atmosphere over a period of 30 minutes, and the mixture was stirred for 1 hour. A solution of n-Bu3SnCl (1.41 mL, 5.0 mmol) in THF was then added dropwise over a period of 30 minutes at -78C, and after stirring for 2 hours, the mixture was raised to room temperature and stirred for another hour. Three drops of a 1N HCl solution were added, and the organic layer was extracted from the aqueous layer twice with 10 mL of ether. The solvent was distilled away to yield the title compound (650 mg, 35 mL). 1H-NMR (Bruker (ARX-300), 300 MHz, CDCl3) delta (ppm): 9.09 (1H, s), 7.88 (1H, s), 1.61-0.87(27H, m). MS (Micromass, Quattromicro, ESI+) m/z: 376.07 (M + 1).
650 mg		Under nitrogen atmosphere, <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> of n-BuLi in hexane solution (4.14, 10mmol) an anhydrous tetrahydrofuran solution of (0.46, 5.0mmol) at -78C added dropwise over 30 minutes, added to 1 hour stirring. n-Bu3SnCl then added dropwise over 30 min a THF solution of (1.41, 5.0mmol) at -78C , stirred for 2 hours, and was heated to room temperature and further stirred for 1 hour. 1N HCl solution was added 3 drops and the organic layer was extracted twice from the aqueous layer with ether 10. The solvent was evaporated to give the title compound (650mg, 35ml).

Reference： [1]Patent: WO2016/168619,2016,A1 .Location in patent: Paragraph 00308
[2]Patent: EP1982982,2008,A1 .Location in patent: Page/Page column 75
[3]Patent: KR101511396,2015,B1 .Location in patent: Paragraph 1050-1053

26
[ 3034-55-7 ]
[ 141-78-6 ]
[ 24295-03-2 ]

Yield	Reaction Conditions	Operation in experiment
87%		To cooled (-78 C) diethyl ether (30ml) was added n-butyllithium (13.2 ml of 2.5M solution in hexanes), followed by the dropwise addition of a solution of 2- bromothiazole (2. 7ml) in diethyl ether (35ml) over 20 minutes. The resulting mixture was stirred for 30 minutes AT-78 C. Under rapid stirring, ethylacetate (5ml) was added over 2-3 minutes. The mixture was stirred for 30 minutes AT-78 C, then allowed to warm to ambient and quenched with saturated sodium bicarbonate solution (50ml). More diethyl ether (50ml) and water (50ml) was added. The organic phase was separated, washed with water and brine, dried with magnesium sulfate, filtered and concentrated. The residue was purified by flash chromatography (20% ethyl acetate/petroleum ether) to afford the sub-title compound as a yellow oil (3.3g, 87%) ; 1H NMR (4OOMHZ, CDC13) o 2.7 (3H, s), 7.65 (1H, s), 8.0 (1H, s); MS (ES+) 128.1 (M+1).

Reference： [1]Patent: WO2004/87699,2004,A2 .Location in patent: Page 82

27
[ 3034-55-7 ]
8-((3,5-dichloropyridin-4-yl)methoxy)-2-methylquinolin-4-ylboronic acid bis-trifluoroacetate [ No CAS ]
[ 76-05-1 ]
(x)C₂HF₃O₂*C₁₉H₁₃Cl₂N₃OS [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2009,vol. 52,p. 4370 - 4379

28
[ 110-91-8 ]
[ 3034-55-7 ]
4-(5-thiazolyl)morpholine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; palladium; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; at 120℃; for 1h;Sealed tube; Inert atmosphere;	General procedure: Using the Pd nanoparticle catalysts obtained in Synthesis Example 1 and Synthesis Example 4, a coupling reaction of a bromothiazole compound and an amine compound was carried out under the conditions shown in Table 5. In the reaction, a bromothiazole compound (0.37 mmol), an amine compound (0.45 mmol), and an amine compoundt-BuONa (0.56 mmol), Pd nanoparticle catalyst (Pd catalyst amount: 3 mol% based on bromothiazole), and 0.5 mL of reaction solvent were added, and the reaction was carried out in a N 2 atmosphere under sealed conditions. The formation of the aminothiazole compound obtained from the reaction was confirmed by gas chromatography and 1 H-, 13 C-NMR spectroscopy. The results are shown in Table 5.

Reference： [1]Organic Letters,2010,vol. 12,p. 1640 - 1643
[2]Patent: JP2018/127451,2018,A .Location in patent: Paragraph 0115; 0117; 0122

29
[ 3034-55-7 ]
[ 5419-55-6 ]
C₁₂H₂₃BNO₃S^(1-)*Li⁽¹⁺⁾ [ No CAS ]

Reference： [1]Organic Letters,2010,vol. 12,p. 2314 - 2317

30
[ 3034-55-7 ]
[ 1200400-56-1 ]
[ 1228092-08-7 ]

Yield	Reaction Conditions	Operation in experiment
6.5%	With salicylaldehyde-oxime; caesium carbonate;copper(I) oxide; In acetonitrile; at 85℃; for 6h;Inert atmosphere; Microwave oven;	b) Preparation of methyl [5-(4-chlorophenyl)-3-methyl-1-(1,3-thiazol-5-yl)-1H-pyrazol-4-yl]acetate Methyl [5-(4-chlorophenyl)-3-methyl-1H-pyrazol-4-yl]acetate (1.0 g, 3.77 mmol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (0.526 g, 3.21 mmol), salicylaldoxime (0.103 g, 0.75 mmol), Cu2O (0.027 g, 0.18 mmol), Cs2CO3 (1.477 g, 4.53 mmol) and acetonitrile (4.8 ml) were introduced successively into a vessel which had been dried by heating and cooled under a stream of argon.The closed vessel was heated in a microwave oven at 85 C. for 6 hours. The reaction mixture was then poured into ice-water and extracted with dichloromethane, and the organic phase was dried and concentrated. Chromatography of the residue gave 0.096 g of product (6.5% of theory); NMR (CDCl3, 400 MHz): 2.31 (s, 3H); 3.35 (s, 2H); 3.70 (s, 3H); 7.22 (d, 2H); 7.29 (br s, 1H); 7.42 (d, 2H); 8.53 (br s, 1H).

Reference： [1]Patent: US2010/197501,2010,A1 .Location in patent: Page/Page column 35

31
[ 3034-55-7 ]
[ 28240-69-9 ]
[ 1242167-11-8 ]

Reference： [1]Journal of Organometallic Chemistry,2010,vol. 695,p. 1891 - 1897

32
[ 3034-55-7 ]
[ 1110642-47-1 ]
(S)-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-3-[(S)-1-(4-thiazol-5-yl-phenyl)-ethyl]-[1,3]oxazinan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; N,N-dimethyl-formamide; at 90℃;Inert atmosphere;	Example 9 (S)-6-(2-Hydroxy-2-methyl-propyl)-6-phenyl-3-[(S)-l-(4-thiazol-5-yl-phenyl)-ethyll-[L31oxazinan-2-one2 M aqueous Na2CO3 solution (0.63 mL) was added to a solution of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (70 muL) and (S)-6-(2-hydroxy-2-methylpropyl)-6-phenyl-3-[(S)-l-(4-(4,4,5,5- tetramethyl- 1,3,2- dioxaborolan-2-yl)phenyl)ethyl]-l,3- oxazinan-2-one (0.30 g) in dimethylformamide (3 mL). The resulting mixture was sparged with argon for 10 min, before [1,1'- bis(diphenylphosphino)ferrocene]dichloro-palladium(II) dichloromethane complex (15 mg) was added. The mixture was heated to 900C and stirred at this temperature for 2 h. After cooling to ambient temperature, water was added, and the resulting mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried (MgSO4), and concentrated. The residue was purified by chromatography on silica gel (cyclohexane/ethyl acetate 50:50->;0:100) to afford the title compound as a solid.Yield: 0.19 g (70% of theory); Mass spectrum (ESI+): m/z = 437 [M+H]+.

Reference： [1]Patent: WO2010/89303,2010,A1 .Location in patent: Page/Page column 52

33
[ 3034-55-7 ]
3-fluoro-4-formylphenylboronic acid [ No CAS ]
[ 1240321-58-7 ]

Reference： [1]Journal of Medicinal Chemistry,2010,vol. 53,p. 6337 - 6354

34
[ 3034-55-7 ]
[ 1253971-78-6 ]
[ 1253971-83-3 ]

Yield	Reaction Conditions	Operation in experiment
12%	With pyridine; caesium carbonate;copper; at 140℃; for 12h;	5-Bromothiazole (2.1 g, 12.8 mmol), l-(6-(2-chloro-4-hydroxyphenoxy)naphthalen-2- yl)ethanone (500 mg, 1.6 mmol), Cs2CO3 (1.56 g, 4.8 mmol), and Cu powder (cat. amount), and pyridine (5 ml) were heated to 140 0C for 12 h. The reaction was quenched with water at cold condition and diluted with DCM (100 ml). The organic layer was washed with IN HCl, water, and brine, dried over sodium sulfate, and concentrated under reduced pressure to afford crude compound which was purified by column chromatography (silica gel 60-120 mesh, 15 % EtOAc-hexane) to give l-(6-(2-chloro-4- (thiazol-5-yloxy)phenoxy)naphthalen-2-yl)ethanone in 12% yield.

Reference： [1]Patent: WO2010/127208,2010,A1 .Location in patent: Page/Page column 96

35
[ 3034-55-7 ]
[ 1256784-52-7 ]
[ 1257300-73-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In ISOPROPYLAMIDE; water; at 90℃; for 1h;	A soluition of tert-butyl 7-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)- 2,3-dihydrobenzo[/][l,4]oxazepine-4(5H)-carboxylate (73 mg, 0.19 mol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (40 mg, 0.26 mmol), 1 , r-Bis(diphenylphosphino)ferrocene] dichloropalladium(II) (22 mg, 0.03 mmol) and potassium carbonate (0.14 g, 1.0 mmol) in JV,iV-dimethylacetamide/water 5:1 (5.5 mL) was heated to 90 0C for lhour. The cooled reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (30 mL) and brine (20 mL), and then dried over anhydrous sodium sulfate and concetrated. Purified by silica gel column chromatography (ethyl acetate/hexanes, 1 :2) to give tert-butyl 7-(thiazol-5-yl)-2,3- dihydrobenzo[/][l,4]oxazepine-4(5H)-carboxylate (44 mg, 70% yield). MS (EI) for Ci7H20N2O3S: 333 (MH+).

Reference： [1]Patent: WO2010/138487,2010,A1 .Location in patent: Page/Page column 161

36
[ 3034-55-7 ]
[ 1263185-90-5 ]
[ 1263186-00-0 ]

Yield	Reaction Conditions	Operation in experiment
	With diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; tributylphosphine; In 1,4-dioxane; toluene; for 16h;Inert atmosphere;	Example 8 ethyl 2-(tert-butyl(3-(3-(thiazol-5-yl)prop-2-ynyloxy)propyl)amino)-2-oxoacetate (8a) A solution of 300 mg of 7f, 330 mg of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>, 300 mul of diisopropyl amine and 200 mul of a 1M solution of tributyl phosphine in toluene, in 4 ml of degassed dioxane was charged with 21 mg of PdCl2 (benzonitrile)2 and 10 mg of CuI. The mixture was stirred under nitrogen atmosphere for 16 hr. The mixture was diluted with 30 ml of 5% NH4Cl and was extracted with ethyl acetate. The organic layer was washed with water, dried, concentrated and the residue was chromatographed over silica gel, using a gradient of heptane/ethyl acetate (1/1) as eluent, to provide 270 mg of N-tert-butyl-N-[3-(3-thiazol-5-yl-prop-2-ynyloxy)-propyl]oxalamic acid ethyl ester 8a, as colorless oil. Rf (heptane/ethyl acetate 1/1) 0.40. NMR (CDCl3) delta 1.35 (t, 3, C2H5), 1.49 (s, 9, tertC4H9), 1.98 (m, 2, CH2), 3.36 (m, 2, CH2), 3.52 (m, 2, CH2), 4.30 (q, 2, C2H5), 4.34 (s, 2, CH2), 7.98 and 8.72 (2*s, 2, thiazole H).
	With tri-tert-butyl phosphine; diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; In 1,4-dioxane; toluene; for 16h;Inert atmosphere;	A solution of 300 mg of 7f, 330 mg of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>, 300 mul of diisopropyl amine and 200 mul of a IM solution of tributyl phosphine in toluene, in 4 ml of degassed dioxane was charged with 21 mg of PdCl2 (benzonitrile)2 and 10 mg of CuI. The mixture was stirred under nitrogen atmosphere for 16 hr. The mixture was diluted with 30 ml of 5% NH4Cl and was extracted with ethyl acetate. The organic layer was washed with water, dried, concentrated and the residu was chromatographed over silica gel, using a gradient of heptane/ethyl acetate (1/1) as eluent, to provide 270 mg of N- tert-butyl-N-[ 3-(3-thiazol-5-yl-prop-2-ynyloxy)-propyl]oxalamic acid ethyl ester 8a, as colorless oil. Rf (heptane/ethyl acetate 1/1) 0.40.NMR (CDCl3) delta 1.35 (t, 3, C2H5), 1.49 (s, 9, tertC4H9), 1.98 (m, 2, CH2), 3.36 (m, 2, CH2), 3.52 (m, 2, CH2), 4.30 (q, 2, C2H5), 4.34 (s, 2, CH2), 7.98 and 8.72 (2x s, 2, thiazole H) .

Reference： [1]Patent: US2011/28450,2011,A1 .Location in patent: Page/Page column 23-24
[2]Patent: WO2011/12600,2011,A1 .Location in patent: Page/Page column 51-52

37
[ 3034-55-7 ]
[ 1263186-27-1 ]
[ 1263186-28-2 ]

Yield	Reaction Conditions	Operation in experiment
	With diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; tri-tert-butyl phosphine; In 1,4-dioxane; toluene; for 16h;Inert atmosphere;	ethyl 2-(tert-butyl(2-(3-(thiazol-5-yl)prop-2-ynyloxy)ethyl)amino)-2-oxoacetate (11e) A solution of 390 mg of 11d, 290 mg of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>, 400 mul of diisopropyl amine, 40 mg of PdCl2(PheCN)2, 20 mg of CuI and 300 mul of a 1M solution of tri-tert-butyl phosphine (in toluene) in 4 ml of degassed dioxane, was stirred under N2 for 16 hr. The mixture was poured into 20 ml of 5% aq. NH4Cl solution and extracted with ethyl acetate. The organic layer was dried, concentrated and the product was chromatographed over silica gel, using a gradient of heptane/ethyl acetate, to give 450 mg of 11e as a colorless oil; Rf 0.40 (heptane/ethyl acetate 1/1); MS-ESI: [M+1] 339.10. NMR (CDCl3) delta 1.48 (s, 9, tertC4H9), 1.35 (t, 3, C2H5), 4.39 (s, 2, CH2) 3.57 (bt, 2, CH2) 4.32 (q, 2, C2H5) 3.68 (bt, 2, CH2), 8.00, 8.72 (2*s, 2, thiazole-H).
	With tri-tert-butyl phosphine; diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; In 1,4-dioxane; toluene; for 16h;Inert atmosphere;	A solution of 390 mg of 1 Id, 290 mg of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>, 400 mul of diisopropyl amine, 40 mg of PdCl2(PheCN)2, 20 mg of CuI and 300 mul of a IM solution of tvi-tert-butyl phosphine (in toluene) in 4 ml of degassed dioxane, was stirred under N2 for 16 hr. The mixture was poured into 20 ml of 5 % aq. NH4C 1 solution and extracted with ethyl acetate. The organic layer was dried, concentrated and the product was chromatographed over silica gel, using a gradient of heptane/ethyl acetate, to give 450 mg of lie as a colorless oil; Rf 0.40 (heptane/ethyl acetate 1/1);MS-ESI: [M+l] 339.10.NMR (CDCl3) delta 1.48 (s, 9, tertC4H9), 1.35 (t, 3, C2H5), 4.39 (s, 2, CH2) 3.57 (bt, 2, CH2) 4.32 (q, 2, C2H5) 3.68 (bt, 2, CH2), 8.00, 8.72 (2x s, 2, thiazole-H).

Reference： [1]Patent: US2011/28450,2011,A1 .Location in patent: Page/Page column 36
[2]Patent: WO2011/12600,2011,A1 .Location in patent: Page/Page column 75

38
[ 3034-55-7 ]
[ 1263186-70-4 ]
[ 1263186-71-5 ]

Yield	Reaction Conditions	Operation in experiment
	With diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; tri-tert-butyl phosphine; In 1,4-dioxane; toluene; for 16h;Inert atmosphere;	ethyl 2-(tert-butyl(6-(thiazol-5-yl)hex-5-ynyl)amino)-2-oxoacetate (17e) A mixture of 180 mg of 17d, 120 mg of purified <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>, 200 mul of diisopropyl amine and 2 ml of degassed dioxane was charged with 150 ml of 1M tri-tert-butyl phosphine (solution in toluene), 20 mg of PdCl2(PheCN)2 and 10 mg of CuI. The mixture was stirred under N2 for 16 hr, and subsequently the reaction mixture was poured into water and extracted with ethyl acetate. The organic extract was washed with water, dried, concentrated and the residue was purified by chromatography over silica gel (using a gradient of heptane/ethyl acetate as eluent) to provide 185 mg of 17e as colorless oil. Rf 0.52 (heptane/ethyl acetate 1/1) NMR (CDCl3) delta 1.34 (t, 3, C2H5), 1.52 (s, 9, tertC4H9), 2.48 (t, 2, CH2), 1.80 (m, 2, CH2) 1.55 (m, 2, CH2), 3.26 (m, 2, CH2) 4.32 (q, 2, C2H5), 7.90 and 8.65 (2*s, 2, thiazole-H).
	With tri-tert-butyl phosphine; diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; In 1,4-dioxane; toluene; for 16h;Inert atmosphere;	A mixture of 180 mg of 17d, 120 mg of purified <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>, 200 mul of diisopropyl amine and 2 ml of degassed dioxane was charged with 150 ml of IM tri- tert-butyl phosphine (solution in toluene), 20 mg of PdCl2(PheCN)2 and 10 mg of CuI. The mixture was stirred under N2 for 16 hr, and subsequently the reaction mixture was poured into water and extracted with ethyl acetate. The organic extract was washed with water, dried, concentrated and the residue was purified by chromatography over silica gel (using a gradient of heptane/ethyl acetate as eluent) to provide 185 mg of 17e as colorless oil.Rf 0.52 (heptane/ethyl acetate 1/1) NMR(CDCl3) delta 1.34 (t, 3, C2H5), 1.52 (s, 9, tertC49), 2.48 (t,2, CH2), 1.80 (m, 2, CH2) 1.55 (m, 2, CH2), 3.26 (m, 2, CH2)4.32 (q, 2, C2H5), 7.90 and 8.65 (2x s, 2, thiazole-H).

Reference： [1]Patent: US2011/28450,2011,A1 .Location in patent: Page/Page column 51
[2]Patent: WO2011/12600,2011,A1 .Location in patent: Page/Page column 104-105

39
[ 3034-55-7 ]
methyl 2-(tert-butyl(hept-6-ynyl)amino)-2-oxoacetate [ No CAS ]
methyl 2-(tert-butyl(7-(thiazol-5-yl)hept-6-ynyl)amino)-2-oxoacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; tri-tert-butyl phosphine; In 1,4-dioxane; toluene; at 20℃;Inert atmosphere;	ethyl 2-(tert-butyl(7-(thiazol-5-yl)hept-6-ynyl)amino)-2-oxoacetate (16i); A solution containing 300 mg of 16h, 180 mul of 5-Br-thiazole, 350 mul of diisopropyl amine, 21 mg of PdCl2(benzonitrile)2, 250 mul of 1M tri-tert-butyl phosphine (in toluene), 12 mg of CuI in 2 ml of degassed dioxane was stirred overnight at RT under a N2 atmosphere. The mixture was poured onto 5% aq. NH4Cl and extracted with ethyl acetate. The extract was dried, concentrated and the crude material was purified by chromatography over silica gel, using a gradient of heptane/ethyl acetate as eluent. This afforded 320 mg 16i as a colorless oil. Rf 0.45 (heptane/ethyl acetate 1/1). MS-ESI: [M+1] 337.17NMR (CDCl3) delta 8.64 and 7.88 (2×s, 2, thiazole H), 1.40 (m, 2, CH2), 1.48 (s, 9, tertC4H9), 1.64 (m, 4, 2×CH2), 2.46 (t, 2, CH2), 3.20 (m, 2, CH2), 3.83 (s, 3, OCH3).

Reference： [1]Patent: US2011/28450,2011,A1 .Location in patent: Page/Page column 48

40
[ 3034-55-7 ]
[ 1263186-58-8 ]
[ 1263186-59-9 ]

Yield	Reaction Conditions	Operation in experiment
	With tri-tert-butyl phosphine; diisopropylamine;copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; In 1,4-dioxane; toluene; at 20℃;Inert atmosphere;	A solution containing 300 mg of 16h, 180 mul of 5-Br-thiazole, 350 mul of diisopropyl amine, 21mg of PdCl2(benzonitrile)2, 250 mul of IM tri-te/t-butyl phosphine (in toluene), 12 mg of CuI in 2 ml of degassed dioxane was stirred overnight at RT under a N2 atmosphere. The mixture was poured onto 5% aq. NH4CI and extracted with ethyl acetate. The extract was dried, concentrated and the crude material was purified by chromatography over silica gel, using a gradient of heptane/ethyl acetate as eluent. This afforded 320 mg 16i as a colorless oil. Rf 0.45 (heptane/ethyl acetate 1/1). MS-ESI: [M+l] 337.17NMR (CDCl3) delta 8.64 and 7.88 (2x s, 2, thiazole H), 1.40 (m, 2, CH2), 1.48 (s, 9, tertC49), 1.64 (m, 4, 2x CH2), 2.46 (t, 2, CH2), 3.20 (m, 2, CH2), 3.83 (s, 3, OCH3).

Reference： [1]Patent: WO2011/12600,2011,A1 .Location in patent: Page/Page column 98

41
[ 3034-55-7 ]
[ 1208318-67-5 ]
[ 1208317-96-7 ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; ethanol; water; toluene; for 5h;Inert atmosphere; Reflux;	To a suspension of 10-2 (1.00 equivalent), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (0.92 equivalent), and sodium bicarbonate (3.15 equivalents) in solvents (DME/H2O/Toluene/EtOH = 10/1/6/3, 4 ml) was added Pd(PPh3)4 (0.2 equivalents). The reaction was degassed, purged with nitrogen and heated to reflux for 5 h. TLC showed that the reaction was complete. Water (4 ml) was added and the mixture was extracted with ethyl acetate (5 ml x 3). The combined organic layers were dried over MgSO4, filtered, concentrated and purified by silica gel column chromatography (DCM : MeOH = 15:1) to afford 10 as a colorless oil.
	With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In 1,2-dimethoxyethane; ethanol; water; toluene; for 5h;Inert atmosphere; Reflux;	Compound 41B (0340) To a suspension of 41A (1.00 equivalent), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (0.92 equivalent), and sodium bicarbonate (3.15 equivalents) in solvents (DME/H2O/Toluene/EtOH=10/1/6/3, 4 mL) was added Pd(PPh3)4 (0.2 equivalents). The reaction was degassed, purged with nitrogen and heated to reflux for 5 h. TLC showed that the reaction was complete. Water (4 mL) was added and the mixture was extracted with ethyl acetate (5 mL×3). The combined organic layers were dried over MgSO4, filtered, concentrated and purified by silica gel column chromatography (DCM:MeOH=15:1) to afford 41B as a colorless oil.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 5849 - 5853
[2]Patent: US9138427,2015,B2 .Location in patent: Page/Page column 274

42
[ 3034-55-7 ]
[ 1068471-18-0 ]
C₁₅H₁₃NO₂S [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2011,vol. 54,p. 6691 - 6703

43
[ 3034-55-7 ]
[ 333-27-7 ]
[ 1341198-70-6 ]

Reference： [1]Polyhedron,2011,vol. 30,p. 2776 - 2782

44
[ 3034-55-7 ]
[ 14548-44-8 ]
[ 1374584-36-7 ]

Reference： [1]Journal of Medicinal Chemistry,2012,vol. 55,p. 4189 - 4204

45
[ 110-89-4 ]
[ 3034-55-7 ]
[ 1388020-57-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; sodium t-butanolate; 1,3-diisopropyl-1H-imidazol-3-ium chloride; In 1,2-dimethoxyethane; at 80℃;Inert atmosphere;	5-Bromothiazole (1.55 g, 9.0 mmol), piperidine (2.7 mL, 27.0 mmol), sodium tert-butoxide (1.78 g, 18.0 mmol), Rh(cod)2BF4 (73 mg, 2.0 mol %), 1,3-diisopropylimidazolium chloride (70 mg, 4.0 mol %) and 1,2-dimethoxyethane (9 mL) were mixed under argon atmosphere. The reaction mixture was vigorously stirred at 80 C overnight, then it was cooled down to room temperature and diluted with AcOEt. The crude reaction was filtered through a pad of silica gel, the organic solvents were evaporated and the residue was purified by flash chromatography on silica gel using as eluent CH2Cl2/AcOEt 10:0.5, then 10:1, to afford a slightly yellow oil (1.40 g; 92%). Found: C 57.49, H 6.92, N 16.48. C8H12N2S requires C 57.11, H 7.19, N 16.65%. IR (Nujol, cm-1): 1651 (CN), 1558 (CC), 1539 (CC). 1H NMR (400 MHz, CDCl3): delta 8.16 (s, 1H), 7.01 (s, 1H), 3.15-3.05 (m, 4H), 1.75-1.68 (m, 4H), 1.60-1.53 (m, 2H). 13C NMR (75 MHz, CDCl3): delta 156.0, 140.5, 122.3, 53.5, 25.1, 23.5. HRMS (ESI+): found 169.0789 [M+H]+. C8H13N2S requires 169.0794.

Reference： [1]Tetrahedron,2012,vol. 68,p. 6427 - 6437

46
[ 3034-55-7 ]
[ 1207557-48-9 ]
[ 1383675-67-9 ]

Yield	Reaction Conditions	Operation in experiment
41%	With bis(di-tert-?butyl(4-?dimethylaminophenyl)?phosphine)?dichloropalladium(II); sodium carbonate; In 1,2-dimethoxyethane; water; at 80℃; for 4h;Inert atmosphere;	General procedure: Reactions were carried out in a Bohdan XT 24 position block using the appropriate halide indicated.2M Sodium carbonate (0.680 mL, 1.36 mmol) was added to a stirred mixture of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazolo[1,5-a]pyridine (10, 151 mg, 0.62 mmol), the appropriate halide (0.74 mmol) and bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (Pd(Amphos)Cl2) (26.3 mg, 0.04 mmol) in DME (4 mL) under nitrogen. The resulting mixture was stirred at 80 C for 4 h, allowed to cool, diluted with water (10 mL), extracted with EtOAc (2×25 mL) and the organic layer was evaporated to afford crude products. Unless otherwise stated the crude product was purified by preparative HPLC (Waters XBridge Prep C18 OBD column, 5 mu silica, 19 mm diameter, 100 mm length, 5-95% MeCN/1% NH3 in H2O).

Reference： [1]Tetrahedron,2012,vol. 68,p. 5434 - 5444

47
[ 3034-55-7 ]
[ 17933-03-8 ]
[ 1396244-67-9 ]

Yield	Reaction Conditions	Operation in experiment
99%	With caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; ethanol; water; at 150℃; under 3750.38 Torr; for 0.25h;Inert atmosphere; microwave irradiation;	A solution of 5-bromo-l,3-thiazole (1 g, 6.10 mmol), m-toy boronic acid (1.244 g, 9.14 mmol), caesium carbonate (5.962 g, 18.30 mmol) and tetrakis(triphenylphosphine) palladium (140 mg, 0.02 eq) in oxygen free DM E/EtOH/water (1 : 1 : 1) (6 m l_) was heated under microwave irradiation at 150C (150 W, 5 bar) for 15 min. The reaction mixture was cooled to rt and quenched with ethyl acetate. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified on silica gel (/7-hexane/ethyl acetate 7 : 3) and afforded the desired product as colourless oil (1.06 g, 99%); MS (ESI) : 176 (M + H)+; IR (cm 1) : 3086, 3026, 2957, 2922, 2862, 1605; *Eta N M R (CD3COCD3) : 2.37 (s, 3H), 7.17 - 7.20 (m, 1H), 7.32 (t, J = 7.7 Hz, 1H), 7.45 - 7.48 (m, 1 H), 7.50 - 7.52 (m, 1 H), 8.19 (s, 1 H), 8.93 (s, 1 H); 13C N M R (CD3COCD3) : 21.4, 124.8, 128.3, 129.99, 130.01, 132.1, 139.8, 140.1, 153.2.
99%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; ethanol; water; at 150℃; for 0.333333h;Sealed tube; Inert atmosphere; Microwave irradiation;	General procedure: In a sealed tube the previously prepared bromo-N-heteroarylcarboxamide derivative (1eq.) was introduced followed by the corresponding boronic acid (1.5eq.), cesium carbonate (3eq.), tetrakis(triphenylphosphine)palladium (0.02eq.) and a mixture of DME/EtOH/H2O (1:1:1, v:v:v, 3mL) as solvent. The reactor was flushed with N2 and submitted to microwave irradiation (150C, 150W) for 20min. After cooling to room temperature, a mixture of EtOAc/H2O (1:1, v:v, 2mL) was added to stop the reaction. The aqueous layer was extracted with EtOAc (3×10mL). The organic layer was washed once with brine and once with water, dried over MgSO4, filtered and the solution was concentrated under reduced pressure. The residue was purified by column chromatography using hexanes and EtOAc as eluant to afford the desired compound.

Reference： [1]Patent: WO2012/117097,2012,A1 .Location in patent: Page/Page column 69
[2]European Journal of Medicinal Chemistry,2014,vol. 83,p. 317 - 337
[3]European Journal of Medicinal Chemistry,2014,vol. 87,p. 203 - 219

48
[ 3034-55-7 ]
[ 1417178-61-0 ]
[ 1417178-62-1 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 9311 - 9316
Angew. Chem.,2012,vol. 124,p. 9445 - 9450,6

49
[ 3034-55-7 ]
[ 1312535-00-4 ]
[ 1312535-01-5 ]

Yield	Reaction Conditions	Operation in experiment
73%	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; for 1h;Reflux;	To a solution of Intermediate IV (80 g, 211.08 mmol) in 1,4-dioxane (800 mL) was added 5- bromo-1,3-thiazole (28 g, 171.78 mmol), Pd(dppf)Cl2 (8 g, 10.62 mmol) and a solution of sodium carbonate (44.7 g, 421.70 mmol) in water (447 mL). The resulting solution was heated to reflux for 1 hour. Then it was allowed to cool and concentrated in vacuo. The residue was diluted with EtOAc (500 mL) and filtered. The filtrate was washed with brine (2x300 mL) and water (2x300 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. The crude product was recrystallized from EtOAc:DCM in the ratio of 1 :5 to get 34 g of product. The mother liquor was applied onto a silica gel column and eluted withdicliloroniethane/ethyl acetate (2:1). This resulted in N-[3-methyl-5-( 1 ,3-thiazol-5-yl)phenyl]-4- (trifluoromethyl)pyrimidin-2-amine (42 g, 125 mmol, 73%) as a pale yellow solid. MS APCI: [M + H]+ m/z 337. 1H NMR (400MHz, CD3COCD3, ppm): 2.413 (3H, s), 7.250-7.263 (2H, m), 7.636 (1H, s), 8.204-8.213 (2H, m), 8.834-8.846 (1H, d, J= 4.8Hz), 8.970 (1H, s), 9.210 (1H, br).
	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; water; for 1h;Reflux;	INTERMEDIATE 21: N-[3-methyl-5-(l,3-thiazol-5-yl)phenyl]-4-(trifluoromethyl)pyrimidin-2- amineTo a solution of N-[3-methyl-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl]-4-(trifluoromethyl)pyrimidin-2-amine (80 g, 211.08 mmol) in 1 ,4-dioxane (800 mL) was added 5- bromo-l ,3-thiazole (28 g, 171.78 mmol), Pd(dppf)Cl2 (8 g, 10.62 mmol) and a solution of sodium carbonate (44.7 g, 421.70 mmol) in water (447 mL). The resulting solution was heated to reflux for 1 hour. Then it was allowed to cool to room temperature and was concentrated in vacuo. The residue was diluted with EtOAc (500 mL) and filtered. The filtrate was washed with brine (2x300 mL) and water (2x300 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. The crude product was recrystallized from EtOAc:DCM in the ratio of 1 :5 to afford a portion of product. The mother liquor was applied onto a silica gel column and eluted with dichloromethane/ethyl acetate (2:1) to afford N-[3-methyl-5-(l,3-thiazol-5- yl)phenyl]-4-(trifluoromethyl)pyrimidin-2-amine as a pale yellow solid. MS ESI calc'd for Ci5H12F3N4S [M + H]+ 337, found 337.. lH NMR (400MHz, CD3COCD3) delta 9.21 (1H, s), 8.97(1H, s), 8.84 (1H, d, J= 4.8Hz), 8.21 (2H, m), 7.64 (1H, s), 7.25-7.26 (2H, m), 2.41 (3H, s). rhSyk activity = +++.

Reference： [1]Patent: WO2011/75560,2011,A1 .Location in patent: Page/Page column 26
[2]Patent: WO2012/154519,2012,A1 .Location in patent: Page/Page column 45-46

50
[ 3034-55-7 ]
[ 1312535-07-1 ]
[ 1312535-10-6 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium fluoride;palladium diacetate; catacxium A; In water; at 75℃;	Step 3: A solution of palladium acetate (19 mg, 0.085 mmol) and butyl di-l -adamantyl phosphine (61 mg, 0.18 mmol) in THF (12.8 mL) was stirred for 15 min. The product from Step 2 (755 mg, 1.70 mmol), 5-bromo-l ,3-thiazole (0.760 ml, 8.50 mmol), potassium fluoride (296 mg, 5.10 mmol), and water (4.25 mL) were then added, and the mixture was heated to 75 C overnight. After cooling to room temperature, the mixture was diluted with EtOAc (100 mL) and washed with brine (100 mL). A bright yellow solid remained undissolved on the walls of the separatory funnel, which was thus rinsed with THF (100 ml). The combined organic extracts were dried over Na2S04, filtered and concentrated in vacuo. The residue was then purified by chromatography on silica gel (100:0 to 50:50 hexanes:EtOAc) to provide N-[3-bromo-5-(l ,3- thiazol-5-yl)phenyl]-4-(trifluoromethyl)pyrimidin-2-amine as an off-white solid. MS ESI calc'd. For Ci4HoBr2F3N4S [M + H]+ 395, 397, 399, found 395, 397, 399.

Reference： [1]Patent: WO2012/154519,2012,A1 .Location in patent: Page/Page column 101

51
[ 3034-55-7 ]
[ 1312535-18-4 ]
[ 1312535-19-5 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 2-methyl-THF; at 100℃;Inert atmosphere;	Step 2: 3-Methyl-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)aniline (20.98 g, 90 mmol), 5- bromothiazole (8.85 mL, 99 mmol) and sodium carbonate (90 mL, 180 mmol) were combined in a flask. 2-Methyl-THF (326 mL) was added and the mixture was degassed with N2 for 1.5 h before l, -bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (3.67 g, 4.50 mmol) was added. The reaction was heated to 100 C overnight and was then cooled to room temperature. The reaction mixture was filtered though a pad of CELITE, washing with ethyl acetate. The layers were separated and the aqueous layer was back-extracted with ethyl acetate, dried over Na2S04, and concentrated. The residue was purified by chromatography on silica gel (0-40% ethyl acetate in hexanes). 3-Methyl-5-(l,3-thiazol-5- yl)aniline was isolated as a yellowish brown solid. MS ESI: [M + H]+ m/z 191. iH NMR (500 MHz, CDCI3) delta 8.71 (s, 1H), 8.02 (s, 1H), 6.80 (s, 1H), 6.71 (s, 1H), 6.50 (s, 1H), 3.71 (s, 2H),
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 2-methyltetrahydrofuran; at 100℃;Inert atmosphere;	[00188] Step 2: 3-Methyl-5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)aniline (20.98 g, 90 mmol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (8.85 mL, 99 mmol) and sodium carbonate (90 mL, 180 mmol) were combined in a flask. 2-Methyl-THF (326 mL) was added and the mixture was degassed with nitrogen for 1.5 hours before 1 , r-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (3.67 g, 4.50 mmol) was added. The reaction was heated to 100 C overnight and was then cooled to room temperature. The reaction mixture was filtered through a pad of Celite, washing with ethyl acetate. The layers were separated and the aqueous layer was back-extracted with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (0- 40% ethyl acetate in hexanes). 3-Methyl-5-(l,3-thiazol-5-yl)aniline was isolated as a yellowish brown solid. MS ESI calc'd. for CioHnN2S [M+H]+ 191, found 191. iH MR (500 MHz, CDC13) delta 8.71 (s, 1H), 8.02 (s, 1H), 6.80 (s, 1H), 6.71 (s, 1H), 6.50 (s, 1H), 3.71 (s, 2H), 1.79 (s, 3H).

Reference： [1]Patent: WO2012/154519,2012,A1 .Location in patent: Page/Page column 38-39
[2]Patent: WO2015/94997,2015,A1 .Location in patent: Paragraph 00188

52
[ 3034-55-7 ]
[ 1312535-03-7 ]
[ 1312535-04-8 ]

Yield	Reaction Conditions	Operation in experiment
93%	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 2-methyltetrahydrofuran; water; at 80℃; for 15h;sealed flask; Inert atmosphere;	Pd(dppf)Cl2 (1.01 g, 1.23 mmol) and Intermediate VII (9.0 g, 25 mmol) were combined in a flask and were evacuated and back-filled with nitrogen (x3). Added 2-Me THF (90 mL), 5- bromothiazole (4.45 g, 27.1 mmol), and aqueous sodium carbonate (24.7 mL, 49.3 mmol) sequentially. Sealed the flask and heated to 80 C for 15 h. The brown solution was allowed to cool to rt, then diluted with water and EtOAc. The layers were separated, and the aqueous portion was extracted with EtOAc (2x). The combined organic portions were washed with saturated aqueous NaHCC>3, then Brine, then dried over Na2S04 and concentrated in vacuo. Trituration with CH2C12 and collection of the beige solid via filtration provided 5.94 g of the desired product. The mother liquor was concentrated in vacuo and subsequent purification via silica gel column chromatography (CH2Cl2-40% EtOAc:CH2Cl2) provided an additional 1.41 g of the desired product. In total, N-[3-(1,3-thiazol-5-yl)phenyl]-4-(trifluoromethyl)pyrimidin-2-amine (7.35 g, 22.8 mmol, 93%) was isolated as a beige solid. MS APCI: [M + H]+ m/z 323. 1H NMR (600 MHz, DMSO-d6, ppm) delta 10.32 (s, 1H), 9.06 (s, 1H), 8.82 (d, J= 4.8 Hz, 1H), 8.20 (d, J= 8.2 Hz, 1H), 8.20 (s, 1H), 7.64 (d, J= 7.5 Hz, 1H), 7.40 - 7.31 (m, 2H), 7.27 (d, J= 4.9 Hz, 1H).

Reference： [1]Patent: WO2011/75560,2011,A1 .Location in patent: Page/Page column 27-28

53
[ 3034-55-7 ]
[ 21789-36-6 ]
[ 1421929-01-2 ]

Yield	Reaction Conditions	Operation in experiment
5%		i-PrMgCl (3.6 mL, 7.2 mmol, 2N solution in THF) was added to a stirred solution of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (972 mg, 6 mmol) in THF (20 mL) at 0 C under nitrogen atmosphere. After stirring at 0 C for 30 min, 2,4-dimethylbenzonitrile (943 mg, 7.2 mmol) was added. The solution was further stirred for 1 h at 0 C, then NaBH4 (456 mg, 12 mmol) was added, followed by addition of MeOH (20 mL). The resulting mixture was allowed to stir at rt overnight, and then NH4Cl (sat.) was added. The resulting mixture was extracted with EtOAc, the combined extracts were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by flash column (petroleum ether/EtOAc = 1/1 to CH2Cl2/MeOH = 50/1) to yield (2,4-dimethylphenyl)(thiazol-5-yl)methanamine (50 mg, yield: 5%). LC-MS (024): m/z = 202.0, [M-NH2]+. Rt = 1.17 min, purity 96.5%

Reference： [1]Patent: WO2013/19621,2013,A1 .Location in patent: Page/Page column 77

54
[ 3034-55-7 ]
[ 942070-45-3 ]
[ 1446474-44-7 ]

Reference： [1]European Journal of Organic Chemistry,2013,p. 4564 - 4569

55
[ 109-99-9 ]
[ 3034-55-7 ]
[ 1451260-66-4 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4600 - 4603

56
[ 123-91-1 ]
[ 3034-55-7 ]
[ 1451260-71-1 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4600 - 4603

57
[ 3034-55-7 ]
[ 201802-67-7 ]
[ 1451736-88-1 ]
[ 1451736-89-2 ]

Reference： [1]Journal of Organic Chemistry,2013,vol. 78,p. 8669 - 8679

58
[ 3034-55-7 ]
[ 1466565-89-8 ]
[ 1466565-24-1 ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; at 20℃; for 3h;Inert atmosphere;	The mixture containing 40% of 244 (0.036 mmol, 1 equiv) was to added to <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (0.22 mmol, 6.0 equiv), sodium carbonate (0.18 mmol, 5.0 equiv) and Pd(dppf)2Cl2 (dichloromethane adduct, 10 mol %) in 2 mL 4:1 (v/v) dioxane-water previously degassed with argon for 15 min. The mixture was stirred for 10 min at room temperature before heating at 88 C. for 2.5 h. The mixture was cooled to room temperature, diluted with 10 mL methylene chloride followed by 10 mL water, and transferred to a separatory funnel. The aqueous layer was extracted with methylene chloride (2×5 mL). The combined organic layers were washed with 2×10 mL water (2×10 mL) and brine (2×10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give 70 mg of crude material, which was purified using flash silica gel chromatography (12 g, ISCO) using a gradient of 0-40% acetone/methylene to provide compound 245. ESI-MS m/z: 570.3 [M+H]+.

Reference： [1]Patent: US2013/267521,2013,A1 .Location in patent: Paragraph 1031

59
[ 3034-55-7 ]
C₃₀H₄₂BN₃O₆ [ No CAS ]
C₁₇H₁₆N₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 2h;Inert atmosphere;	A 25-mL round bottom flask equipped with a magnetic stirrer, a condenser and anitrogen inloutlet adapter was charged with 55a (40 mg, 0.07 mmol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (14 mg,0.09 mmol), water/dioxane (1 mL/3 ml), K2C03 (20 mg, 0.14 mmol). The resulting solution wasdegassed for 5 minutes, then Pd(PPh3)4 (10 mg, 0.009 mmol) was added. The reaction mixturewas heated to 100 C for 2 hours. After being allowed to cool to room temperature, the reactionmixture was diluted with EtOAc (30 mL) and washed with saturated NaHCO3 (10 mL), brinemL), dried over Na2SO4. The organic layer was concentrated under reduced pressure andpurified on silica gel. Elution with 10% EtOAc/hexanes afforded the title compound (25 mg,68%) as a white solid. ?H NMR (CDC13, 300 MHz) 9.47 (broad s, 1H), 9.32 (broad s, JH),8.78 (s, 111), 8.11 (s, 1H), 7.56-7.66 (m, 5H), 7.50 (d, 1H, J= 7.80Hz), 7.39 (t, 1H, J= 7.50Hz), 7.25 (d, 1H,J? 7.50 Hz), 5.21 (s, 2H), 1.50 (s, 9H), 1.35 (s, 9H).

Reference： [1]Patent: WO2013/106761,2013,A2 .Location in patent: Page/Page column 111

60
[ 3034-55-7 ]
2,5-bis(tributylstannyl)thiophene 1,1-dioxide [ No CAS ]
2,5-di(thiazol-5-yl)thiophene 1,1-dioxide [ No CAS ]

Reference： [1]Organic Letters,2013,vol. 15,p. 5230 - 5233

61
[ 3034-55-7 ]
[ 50978-45-5 ]
C₄H₂FNOS [ No CAS ]

Reference： [1]Organic Letters,2013,vol. 15,p. 5370 - 5373

62
[ 616-45-5 ]
[ 3034-55-7 ]
[ 1572031-55-0 ]

Reference： [1]Chemical Communications,2014,vol. 50,p. 3163 - 3165

63
[ 3034-55-7 ]
[ 1616828-84-2 ]
[ 1616830-13-7 ]

Yield	Reaction Conditions	Operation in experiment
26%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In water; N,N-dimethyl-formamide; at 80 - 100℃;Sealed tube;	a) 6- (Thiazol-5-yl)- 8-((2- (trimethylsilyl)ethoxy)methoxy)-3- ((2-(trimethylsilyl)ethoxy)methyl)guinazolin-4(3H)-oneA suspension of <strong>[3034-55-7]5-bromo-thiazole</strong> (0.02g, 0.1 mmol), (6-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-8- ((2- (trimethylsilyl)ethoxy)methoxy)-3-((2- (trimethylsilyl)ethoxy)methyl)quinazolin-4(3H)-one (0.05 g, 0.08 mmol, example 28), bis (diphenylphosphino)feffocene-palladium(II)dichloride (0.01 g, 0.01 mmol), potassiumcarbonate (0.03 g, 0.25 mmol) and water (0.2 ml) in dimethylformamide (1 ml) was stirred in a sealed tube at 100 C for 2 hours and then at 80 C overnight. Filtration and chromatography (C18 reverse phase HPLC, methanol / water = 40:60 to 100:0) yielded the title compound as white solid (0.01 g, 26 %). MS: mle = 506.7 [M+Hf?.

Reference： [1]Patent: WO2014/102233,2014,A1 .Location in patent: Page/Page column 115

64
[ 3034-55-7 ]
[ 1594127-49-7 ]
[ 1616400-79-3 ]

Yield	Reaction Conditions	Operation in experiment
22%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 16h;	A mixture of 11 (200 mg, 0.64 mmol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (157 mg, 0.96 mmol), potassium carbonate (177 mg, 1.28 mmol), tetrakis(triphenylphosphine)palladium(0) (38 mg, 0.04 mmol), dioxane (6 mL) and water (1 mL) was heated at 90 C. for 16 h. The reaction mixture was cooled and concentrated under reduced pressure. The residue was purified by chromatography (silica gel, 0-100% EtOAc in hexanes) to provide Example 80 (38 mg, 22%) as a white solid: 1H NMR (500 MHz, CDCl3) delta 8.69 (s, 1H), 7.82 (s, 1H), 7.53 (dd, J=2.1, 9.1 Hz, 1H), 7.50 (d, J=2.4 Hz, 1H), 7.38-7.32 (m, 5H), 6.71 (d, J=9.5 Hz, 1H), 5.12 (s, 2H); ESI MS m/z 269 [M+H]+.

Reference： [1]Patent: US2014/179648,2014,A1 .Location in patent: Paragraph 0755; 0756

65
[ 3034-55-7 ]
[ 5765-65-1 ]
[ 933728-73-5 ]

Reference： [1]Angewandte Chemie - International Edition,2014,vol. 53,p. 4667 - 4670
Angew. Chem.,2014,vol. 126,p. 4755 - 4758,4

66
[ 3034-55-7 ]
[ 1020657-86-6 ]
9-ethyl-3-thiazol-5-yl-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 90℃; for 16h;	[0111] A biphasic mixture of 9-ethyl-3-(4,4,5,5-tetramethyl-[l,3,2]dioxaborolan-2- yl)-9H-carbazole (100 mg, 0.31 mmol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (102 mg, 56 mu,, 0.62 mmol), te£raHs(triphenylphosphine)palladium(0) (29 mg, 0.025 mmol), aqueous potassium carbonate (2 M, 310 mu, 0.62 mmol) in ethanol (0.8 mL) and toluene (0.4 mL) was stirred at 90 C for 16 h. The mixture was evaporated and the residue was purified by column chromatography eluting with hexane:ethyl acetate (9: 1). The solid was triturated with hexane (1 mL) to give the title compound (46 mg, 0.17 mmol, 53%) as a white powder. LCMS: 97%, Rt 1.884, ESMS m/z 279 (M+H)+; XH NMR (400 MHz, CDC13) delta ppm 8.74 (s, 1H), 8.28 (d, J= 1.5 Hz, 1H), 8.14 (d, J= 7.8 Hz, 1H), 8.11 (s, 1H), 7.69 (dd, J= 8.4, 1.6 Hz, 1H), 7.50 (t, J= 7.5 Hz, 1H), 7.39 - 7.45 (m, 2H), 7.27 (t, J= 7.2 Hz, 1H), 4.39 (q, J= 7.2 Hz, 2H), 1.46 (t, J= 7.3 Hz, 3H).

Reference： [1]Patent: WO2014/153043,2014,A1 .Location in patent: Paragraph 0110-0111

67
[ 3034-55-7 ]
[ 5720-07-0 ]
[ 68535-58-0 ]

Yield	Reaction Conditions	Operation in experiment
5.1 g	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In 1,2-dimethoxyethane; water; at 80℃;	Step 1: 5-(4-Methoxyphenyl)thiazole[00375] A mixture of (4-methoxyphenyl)boronic acid (7 g, 45.7 mmol), <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (5g, 30.5 mmol), potassium carbonate (8.4 g, 61 mmol), and PdCl2(PPh3)2(2.1 g, 3 mmol) in DME/water (5:1, 60 mL) was heated to 80C overnight. After cooling, ethyl acetate and brine were added to the reaction mixture and the two layers were separated. The organic layer was washed with more brine, dried over sodium sulfate, and filtered. The organic layer was evaporated to dryness. The residue was purified by flash chromatography on silica gel to afford 5.1g of 5-(4-methoxyphenyl)thiazole as a yellow solid. 1H NMR (400 MHz, DMSO-d6): delta 9.00 (s, 1H), 8.18 (s, 1H), 7.60 (d, 2H), 7.00 (d, 2H), 3.79 (s, 3H).
	With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate; In 1,4-dioxane; water; at 90℃;Inert atmosphere;	Step 1: preparation of 5-(4-methoxyphenyl)thiazole To a 100mL single-neck flask were added 2.2g p-methoxyphenylboronic acid(0.014mol), 2g <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong>(0.012mol), 7.8g cesium carbonate(0.024mol) and 0.4g bis(triphenylphosphine)palladium dichloride(0.6mmol), then added 30mL 1,4-dioxane and 8mL water. The mixture was heated to 90C under nitrogen protection, and was reacted overnight. The reaction was stopped after the starting materials were almost reacted completely. The mixture was cooled to room temperature, concentrated, and extracted with water and ethyl acetate. The organic phases were combined, dried, concentrated, and separated by silica gel column chromatography to give a pale yellow solid product. 1HNMR(300MHz,CDCl3)delta:8.74(s,1H,Ar-H), 8.00(s,1H,Ar-H),7.51-7.54(m,2H, Ar-H), 6.95-6.99 (m,2H, Ar-H),3.87(s,3H,OCH3). ESI-MS m/z: [M+H]+ =192.2.

Reference： [1]Patent: WO2014/151899,2014,A1 .Location in patent: Paragraph 00375
[2]Patent: EP2940031,2015,A1 .Location in patent: Paragraph 0087

68
[ 3034-55-7 ]
(R)-tert-butyl-1-(3-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylamino)-4-methyl-1-oxopentan-2-yl-carbamate [ No CAS ]
(R)-tert-butyl-1-(3-methoxy-4-(thiazol-5-yl)phenylamino)-4-methyl-1-oxopentan-2-yl-carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium phosphate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 100℃; for 4h;Inert atmosphere;	5 -Bromothiazole (23.50 mg, 0.143 mmol), (R)-tert-butyl 1 -(3 -methoxy-4- (4,4,5,5 -tetramethyl- 1,3 ,2-dioxaborolan-2-yl)phenylamino)-4-methyl- 1 -oxopentan-2- ylcarbamate (53 mg, 0.115 mmol), potassium phosphate (97 mg, 0.458 mmol), anddioxane were combined in a conical vial. Nitrogen was bubbled through the reaction mixture for several mi Dichloro[ 1,1 ?-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct (9.43 mg, 0.011 mmol) was added and the reaction mixture was heated at 100 C for 4 h. The reaction mixture was cooled to room temperature and was transferred to a separatory funnel containing saturated aqueousNaHCO3 solution (2 mL). The aqueous layer was extracted with ethyl acetate (3 X 5 mL). The combined organic layers were washed with brine (2 mL), dried over MgSO4, filtered and concentrated. The residue was purified by column chromatography on silica gel (20% -* 60% ethyl acetate in hexanes) to afford (R)tert-butyl 1 -(3 -methoxy-4-(thiazol-5 -yl)phenylamino)-4-methyl- 1 -oxopentan-2-ylcarbamate (31 mg, 65% yield) as a colorless amorphous solid: ?H NMR (400 MHz, DMSO-d6) oe 10.15 (s, 1 H), 9.02 (s, 1 H), 8.31 (s, 1 H), 7.71 (d, J=8.6 Hz, 1 H), 7.53 (d, J2.0 Hz, 1 H), 7.31 (dd, J8.4, 1.9 Hz, 1 H), 7.08 (d, J=8.1 Hz, 1 H), 4.09 - 4.17 (m, 1 H), 3.89 (s, 3 H), 1.61 - 1.72 (m, 1 H), 1.48- 1.59 (m, 1 H), 1.42- 1.47 (m, 1H), 1.38 (s, 9 H), 0.90 (d, J=6.3 Hz, 3 H), 0.90 (d, J=6.5 Hz, 3 H); LC/MS (ESI) m/e420.2 [(M+H), calcd for C2,H30N304S 420.2].

Reference： [1]Patent: WO2015/6100,2015,A1 .Location in patent: Page/Page column 90; 91

69
[ 3034-55-7 ]
[ 1637279-85-6 ]
2-(5-thiazolyl)-5-(1-perfluorohexyl)thiophene [ No CAS ]

Reference： [1]Chemistry of Materials,2014,vol. 26,p. 6542 - 6556

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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. 3034-55-7 ]

Quality Control of [ 3034-55-7 ]

Related Doc. of [ 3034-55-7 ]

Product Details of [ 3034-55-7 ]

Calculated chemistry of [ 3034-55-7 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 3034-55-7 ]

Application In Synthesis of [ 3034-55-7 ]

[ 3034-55-7 ] Synthesis Path-Upstream 1~8

[ 3034-55-7 ] Synthesis Path-Downstream 1~69

Related Functional Groups of [ 3034-55-7 ]

Bromides

Related Parent Nucleus of [ 3034-55-7 ]

Thiazoles

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 3034-55-7 ]

Related Parent Nucleus of
[ 3034-55-7 ]