[ CAS No. 6163-58-2 ] {[proInfo.proName]}

Name: 6163-58-2|Tri-o-tolylphosphine|98%
Brand: Ambeed
SKU: A341207
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2D 3D

Structure of 6163-58-2 * Storage: {[proInfo.prStorage]}

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Quality Control of [ 6163-58-2 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 6163-58-2 ]

SDS Specification

Alternatived Products of [ 6163-58-2 ]

Product Details of [ 6163-58-2 ]

CAS No. :	6163-58-2	MDL No. :	MFCD00008514
Formula :	C₂₁H₂₁P	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	COIOYMYWGDAQPM-UHFFFAOYSA-N
M.W :	304.37	Pubchem ID :	80271
Synonyms :

Calculated chemistry of [ 6163-58-2 ]

Physicochemical Properties

Num. heavy atoms :	22
Num. arom. heavy atoms :	18
Fraction Csp3 :	0.14
Num. rotatable bonds :	3
Num. H-bond acceptors :	0.0
Num. H-bond donors :	0.0
Molar Refractivity :	100.05
TPSA :	13.59 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.11 cm/s

Lipophilicity

Log Po/w (iLOGP) :	3.73
Log Po/w (XLOGP3) :	5.7
Log Po/w (WLOGP) :	4.37
Log Po/w (MLOGP) :	5.85
Log Po/w (SILICOS-IT) :	6.99
Consensus Log Po/w :	5.33

Druglikeness

Lipinski :	1.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-5.73
Solubility :	0.000573 mg/ml ; 0.00000188 mol/l
Class :	Moderately soluble
Log S (Ali) :	-5.75
Solubility :	0.000539 mg/ml ; 0.00000177 mol/l
Class :	Moderately soluble
Log S (SILICOS-IT) :	-8.69
Solubility :	0.000000621 mg/ml ; 0.000000002 mol/l
Class :	Poorly soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	4.09

Safety of [ 6163-58-2 ]

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

Application In Synthesis of [ 6163-58-2 ]

* 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 [ 6163-58-2 ]
Downstream synthetic route of [ 6163-58-2 ]

[ 6163-58-2 ] Synthesis Path-Upstream 1~19

1
[ 95-46-5 ]
[ 6163-58-2 ]

Reference： [1] Dalton Transactions, 2017, vol. 46, # 27, p. 8827 - 8838
[2] Organic Letters, 2017, vol. 19, # 3, p. 694 - 697
[3] Organometallics, 2013, vol. 32, # 22, p. 6736 - 6744
[4] Journal of Organic Chemistry, 1978, vol. 43, p. 2941 - 2946
[5] Canadian Journal of Chemistry, 1982, vol. 60, p. 716 - 722

2
[ 6163-63-9 ]
[ 6163-58-2 ]

Yield	Reaction Conditions	Operation in experiment
89%	at 20℃; for 4 h;	General procedure: To a mixture of Mg powder (8 mmol, 4 mol equiv), Me3SiCl (6 mmol, 3 mol equiv), and DMI (8 mL) was added 2a (2 mmol), and the whole mixture was stirred for 2 h at room temperature. To the reaction mixture was added satd aq (NH4)2CO3, and the mixture was extracted with Et2O (10 mL 3). The combined organic layers were washed with satd aq NaCl, dried over Na2SO4, and concentrated under reduced pressure. The resultant was analyzed by 31P NMR to find that 1a and 2a were obtained in 97:3 ratio. The desired 1a was obtained in 96percent yield after purification by silica gel column chromatography (hexane/AcOEt = 5:1) (Table 1, entry 1).

Reference： [1] Tetrahedron Letters, 2015, vol. 56, # 7, p. 918 - 920
[2] Synthesis, 2011, # 24, p. 4091 - 4098
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 46, p. 15253 - 15256[4] Angew. Chem., 2018, vol. 130, # 46, p. 15473 - 15476,4

3
[ 172418-37-0 ]
[ 15475-27-1 ]
[ 6163-58-2 ]

Yield	Reaction Conditions	Operation in experiment
20%	Stage #1: at 20℃; for 48 h; Schlenk technique; Inert atmosphere Stage #2: With air In tetrahydrofuran for 48 h; Schlenk technique	Complex 1d (0.1636g, 0.2659mmol) was added to an oven dried Ar-filled 50-mL Schlenk flask containing a magnetic stirring bar. The flask was evacuated and filled with Ar 5 times. Then abs. THF (17mL) was added followed by a 0.5M solution of KPPh₂ in THF (3.2mL, 1.6mmol). During the dropwise addition, the orange solution turned dark red, and then black. The mixture was stirred at rt for 48h in Ar. The reaction mixture was then filtered through celite (h=1cm), and the flask with the filtrate was placed on a rotavapor to remove solvent. The crude product was dissolved in CH₂Cl₂ and separated into several fractions using preparative TLC (10:1 ethyl acetateacetone). Fraction 1 corresponded to 8-methylquinoline 7d (0.0450g, 0.314mmol, 48percent, colorless oil). Fraction 3 corresponded to compound 8d (0.0321g, 0.0231mmol, 21percent, colorless oil). R_f 0.40 (10:1 ethyl acetateacetone). ¹H NMR (δ, ppm): 4.56 (d, 2H, ²J_H,P=14.2, PCH₂), 7.28 (t, 1H, ³J_H,H=4.2, arom. H(3)), 7.31 (m, 4H, o-PPh), 7.38 (dt, 2H, ³J_H,H=7.4, ⁴J_H,H=1.3, p-PPh), 7.46 (t, 1H, ²J_H,P=15.4, arom. H(6)), 7.64 (d, 1H, ³J_H,P=8.2, arom. H(7)), 7.78 (m, 4H, m-PPh), 8.03 (dd, 1H, ³J_H,H=8.2, ⁵J_H,H=1.6, arom. H(5)), 8.05 (m, 1H, arom. H(4)), 8.76 (dd, 1H, ³J_H,H=4.1, ⁵J_H,H=1.6, arom. H(2)). ¹³C{¹H} NMR (δ, ppm): 21.2 (d, ¹J_C,P=67.9, PCH₂), 121.2 (s, arom. CH(3)), 126.8 (d, ³J_C,P=2.8, arom. CH(6)), 127.2 (d, ⁴J_C,P=1.0, arom. CH(7)), 128.5 (d, ²J_C,P=11.6, o-PPh), 131.2 (d, ²J_C,P=7.7, ipso-PPh), 131.55 (s, arom. CH(5)), 131.56 (d, ²J_C,P=9.2, m-PPh), 131.8 (d, ²J_C,P=2.3, p-PPh), 133.0 (s, arom. C(10)), 133.8 (two s, (s, arom. CH(8)), 136.6 (s, arom. CH(4)), 146.7 (d, ²J_C,P=5.5, arom. CH(9)), 149.4 (s, CH, arom. CH(2)). ³¹P{¹H} NMR (CDCl₃, δ, ppm): 16.5. IR (Nujol mull, ν, cm⁻¹): 1199s(P=O). HRMS: [M+ H]⁺ calcd for C₂₂H₁₉NOP 343.1199, found 344.1108.

Reference： [1] Journal of Organometallic Chemistry, 2015, vol. 797, p. 13 - 20

4
[ 15475-27-1 ]
[ 6163-58-2 ]

Yield	Reaction Conditions	Operation in experiment
2%	Stage #1: at 20℃; for 48 h;	Complex 1d (0.1636g, 0.2659mmol) was added to an oven dried Ar-filled 50-mL Schlenk flask containing a magnetic stirring bar. The flask was evacuated and filled with Ar 5 times. Then abs. THF (17mL) was added followed by a 0.5M solution of KPPh₂ in THF (3.2mL, 1.6mmol). During the dropwise addition, the orange solution turned dark red, and then black. The mixture was stirred at rt for 48h in Ar. The reaction mixture was then filtered through celite (h=1cm), and the flask with the filtrate was placed on a rotavapor to remove solvent. The crude product was dissolved in CH₂Cl₂ and separated into several fractions using preparative TLC (10:1 ethyl acetateacetone). Fraction 1 corresponded to 8-methylquinoline 7d (0.0450g, 0.314mmol, 48percent, colorless oil). Fraction 3 corresponded to compound 8d (0.0321g, 0.0231mmol, 21percent, colorless oil). R_f 0.40 (10:1 ethyl acetateacetone). ¹H NMR (δ, ppm): 4.56 (d, 2H, ²J_H,P=14.2, PCH₂), 7.28 (t, 1H, ³J_H,H=4.2, arom. H(3)), 7.31 (m, 4H, o-PPh), 7.38 (dt, 2H, ³J_H,H=7.4, ⁴J_H,H=1.3, p-PPh), 7.46 (t, 1H, ²J_H,P=15.4, arom. H(6)), 7.64 (d, 1H, ³J_H,P=8.2, arom. H(7)), 7.78 (m, 4H, m-PPh), 8.03 (dd, 1H, ³J_H,H=8.2, ⁵J_H,H=1.6, arom. H(5)), 8.05 (m, 1H, arom. H(4)), 8.76 (dd, 1H, ³J_H,H=4.1, ⁵J_H,H=1.6, arom. H(2)). ¹³C{¹H} NMR (δ, ppm): 21.2 (d, ¹J_C,P=67.9, PCH₂), 121.2 (s, arom. CH(3)), 126.8 (d, ³J_C,P=2.8, arom. CH(6)), 127.2 (d, ⁴J_C,P=1.0, arom. CH(7)), 128.5 (d, ²J_C,P=11.6, o-PPh), 131.2 (d, ²J_C,P=7.7, ipso-PPh), 131.55 (s, arom. CH(5)), 131.56 (d, ²J_C,P=9.2, m-PPh), 131.8 (d, ²J_C,P=2.3, p-PPh), 133.0 (s, arom. C(10)), 133.8 (two s, (s, arom. CH(8)), 136.6 (s, arom. CH(4)), 146.7 (d, ²J_C,P=5.5, arom. CH(9)), 149.4 (s, CH, arom. CH(2)). ³¹P{¹H} NMR (CDCl₃, δ, ppm): 16.5. IR (Nujol mull, ν, cm⁻¹): 1199s(P=O). HRMS: [M+ H]⁺ calcd for C₂₂H₁₉NOP 343.1199, found 344.1108.

Reference： [1] Journal of Organometallic Chemistry, 2015, vol. 797, p. 13 - 20

5
[ 64-17-5 ]
[ 878809-28-0 ]
[ 150-46-9 ]
[ 6163-58-2 ]

Reference： [1] Tetrahedron, 2009, vol. 65, # 32, p. 6410 - 6415

6
[ 932-31-0 ]
[ 6163-58-2 ]

Reference： [1] Journal of the Chemical Society, 1937, p. 527,530

7
[ 1094249-98-5 ]
[ 148892-95-9 ]
[ 6163-58-2 ]

Reference： [1] Organometallics, 2010, vol. 29, # 16, p. 3647 - 3654

8
[ 1094249-98-5 ]
[ 148892-95-9 ]
[ 1333-74-0 ]
[ 6163-58-2 ]

Reference： [1] Organometallics, 2010, vol. 29, # 16, p. 3647 - 3654
[2] Organometallics, 2010, vol. 29, # 16, p. 3647 - 3654

9
[ 74-85-1 ]
[ 1073-39-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 99717-87-0 ]

Reference： [1] Patent: US4724260, 1988, A,

10
[ 54446-36-5 ]
[ 6163-58-2 ]
[ 201802-67-7 ]
[ 167218-30-6 ]

Yield	Reaction Conditions	Operation in experiment
49%	With magnesium sulfate; potassium carbonate In ethanol; toluene	[Step 2] Synthesis of N,N',N'-triphenylbenzidine (abbreviation: DPBA) A synthesis scheme of N,N',N'-triphenylbenzidine (abbreviation: DPBA) is shown in (H-2). 4.3 g (17 mmol) of 4-bromodiphenylamine, 5 g (17 mmol) of triphenylamine-4-boronic acid, and 532 mg of tri(o-tolyl)phosphine were put into a 500 mL three-neck flask, and the atmosphere in the flask was substituted by nitrogen. 60 mL of toluene, 40 mL of ethanol, and 14 ml of a potassium carbonate aqueous solution (0.2 mol/L) were added into this mixture. The mixture was deaerated while being stirred under reduced pressure, and after deaeration, 75 mg (0.35 mmol) of palladium(II) acetate was added. This mixture was refluxed at 100° C. for 10.5 hours. An aqueous layer of the mixture was extracted with toluene. The extracted solution and an organic layer were washed together with saturated brine, and magnesium sulfate was added thereto for drying. This mixture was filtrated and the filtrate was concentrated to obtain an oily light-brown substance. The oily substance was dissolved in about 50 mL of toluene, and was subjected to suction filtration through Celite (manufactured by Celite Co., Ltd.), alumina, and Florisil (manufactured by Floridin Company). A solid substance obtained by concentrating the filtrate was purified by a silica gel column chromatography (developing solvent was a mixed solvent of hexane:toluene=4:6) to obtain a white solid substance. The obtained white solid substance was recrystallized with chloroform/hexane, so that 3.5 g of an white substance was obtained in yield 49percent.

Reference： [1] Patent: US2009/4506, 2009, A1,

11
[ 54446-36-5 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 201802-67-7 ]
[ 167218-30-6 ]

Yield	Reaction Conditions	Operation in experiment
49%	With magnesium sulfate; potassium carbonate In ethanol; toluene	[Step 5] Synthesis of N,N',N'-triphenylbenzidine A synthesis scheme of N,N',N'-triphenylbenzidine is shown in (a-6). Into a 500 mL three-neck flask were put 4.3 g (17 mmol) of 4-bromodiphenylamine, 5 g (17 mmol) of triphenylamine-4-boronic acid, and 532 mg (1.8 mmol) of tri(o-tolyl)phosphine, and the atmosphere in the flask was replaced with nitrogen. Then, 60 mL of toluene, 40 mL of ethanol, and 14 mL of potassium carbonate aqueous solution (0.2 mol/L) were added to this mixture. After this mixture was degassed under reduced pressure, 75 mg (0.35 mmol) of palladium (II) acetate was added. This mixture was refluxed at 100° C. for 10.5 hours. After the reflux, the aqueous layer of the mixture was extracted with toluene. The extracted solution was combined with an organic layer and washed with a saturated saline, and magnesium sulfate was added thereto for drying. This mixture was filtered and the filtrate was concentrated to give an oily light-brown substance. The oily substance was dissolved in toluene of about 50 mL, and then subjected to suction filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135). A solid obtained by concentrating the filtrate was purified by a silica gel column chromatography (developing solvent was a mixed solvent of hexane:toluene 4:6) to give a white solid. The obtained white solid was recrystallized with chloroform/hexane, so that 3.5 g of a white solid was obtained in a yield of 49percent.

Reference： [1] Patent: US2010/51926, 2010, A1,

12
[ 6163-58-2 ]
[ 40691-33-6 ]

Reference： [1] Journal of Organometallic Chemistry, 2008, vol. 693, # 6, p. 1117 - 1126
[2] Patent: CN103772444, 2016, B, . Location in patent: Paragraph 0209; 0210; 0215; 0221; 0226; 0231; 0236

13
[ 6163-58-2 ]
[ 69861-71-8 ]

Yield	Reaction Conditions	Operation in experiment
98%	for 3 h; Heating / reflux	Palladium tetrammine dihydrogencarbonate was reacted with 3 mole equivalents of tris(orffto- tolyl)phosphine (Po-tol₃) in methanol at reflux under N₂ for 3 hours. The reaction mixture was cooled to O⁰C and filtered to give product as bright yellow crystal. The filtrate was evaporated to 10ml, and filtered to give more yellow precipitate. Total yield = 98percent. NMR and IR indicate pure product as Pd(Po-tol₃)₂ (Pd(O)).

Reference： [1] Patent: WO2007/29031, 2007, A1, . Location in patent: Page/Page column 5

14
[ 52409-22-0 ]
[ 6163-58-2 ]
[ 69861-71-8 ]

Reference： [1] Organometallics, 2013, vol. 32, # 12, p. 3570 - 3573

15
[ 6163-58-2 ]
[ 32005-36-0 ]
[ 69861-71-8 ]

Reference： [1] Journal of the American Chemical Society, 1994, vol. 116, # 13, p. 5969 - 5970
[2] Journal of the American Chemical Society, 2017, vol. 139, # 34, p. 11662 - 11665

16
[ 6163-58-2 ]
[ 69861-71-8 ]

Reference： [1] Organometallics, 1995, vol. 14, p. 3030 - 3039

17
[ 40691-33-6 ]
[ 6163-58-2 ]
[ 69861-71-8 ]

Reference： [1] European Journal of Inorganic Chemistry, 1998, # 1, p. 29 - 35

18
[ 854952-58-2 ]
[ 1592-95-6 ]
[ 6163-58-2 ]
[ 1060735-14-9 ]

Reference： [1] Patent: US8231942, 2012, B2,

19
[ 6163-58-2 ]
[ 954137-48-5 ]

Reference： [1] Patent: US2015/255720, 2015, A1,

[ 6163-58-2 ] Synthesis Path-Downstream 1~87

1
[ 17117-17-8 ]
[ 252870-83-0 ]
[ 6163-58-2 ]
[ 252870-59-0 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In acetonitrile;	Under a nitrogen atmosphere, a mixture of <strong>[17117-17-8]5-ethoxy-3-bromopyridine</strong> (1.20 g, 5.94 mmol), N-methyl-N-(tert-butoxycarbonyl)-4-penten-2-amine (1.18 g, 5.94 mmol), palladium(II) acetate (13.5 mg, 0.06 mmol), tri-o-tolylphosphine (73.1 mg, 0.24 mmol), triethylamine (1.5 mL, 10.8 mmol), and anhydrous acetonitrile (3 mL) was stirred and heated under reflux at 80-85 C. for 28 h. The resulting mixture, containing beige solids, was cooled to ambient temperature, diluted with water (20 mL), and extracted with CHCl3 (3*20 mL). The combined light-yellow CHCl3 extracts were dried (Na2SO4), filtered, concentrated by rotary evaporation, and vacuum dried producing a yellow oil (1.69 g). The crude product was purified by column chromatography on silica gel (100 g), eluding with ethyl acetate-hexane (1:1, v/v). Selected fractions containing the product (Rf 0.20) were combined, concentrated by rotary evaporation, and the residue was vacuum dried to give 0.67 g (35.2%) of a light-yellow oil. (4E)-N-Methyl-5-(5-ethoxy-3-pyridyl)-4-penten-2-amine

Reference： [1]Patent: US6979695,2005,B2

2
[ 7169-97-3 ]
[ 6163-58-2 ]
[ 207922-53-0 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In acetonitrile; at 85℃; under 2585.81 Torr; for 66h;	A solution of of N-(5-bromo-pyridin-2-yl)-acetamide (prepared as described in Preparation One, 4.30 g, 20 mmol) in acetonitrile (15 ml) and triethylamine (5.04 ml) was treated with palladium acetate (45 mg, 0.2 mmol) and tri-o-tolylphosphine (203 mg, 0.66 mmol). The mixture was placed in a pressure reactor under 50 psig of ethylene pressure and heated at 85 C. for 66 hours. The reaction mixture was cooled, vented, and partitioned between phosphate buffer (0.1M, pH 6.6) and ethyl acetate. The aqueous phase was extracted with ethyl acetate twice more. The combined ethyl acetate extracts were washed with additional phosphate buffer, brine and dried over sodium sulfate. The extracts were filtered and evaporated to afford 2.06 g (63%) of the title product as a flaky crystalline residue. Recrystallization from ethyl acetate/cyclohexane gave colorless flakes. mp 120-121 C. 1H NMR (CDCl3): delta=8.55 (br, 1H); 8.24 (d, 1H); 8.15 (d, 1H); 7.76 (d of d, 1H); 6.64 (d of d, 1H); 5.73 (d, 1H); 5.28 (d, 1H); 2.19 (s, 3H). MS (CI): m/z=163 (M+H+).
2.06 g (63%)	With triethylamine;palladium diacetate; In ethene; acetonitrile;	Example One N-(5-Vinyl-pyridin-2-yl)-acetamide. A solution of of N-(5-bromo-pyridin-2-yl)-acetamide (4.30 g, 20 mmol) in acetonitrile (15 ml) and triethylamine (5.04 ml) was treated with palladium acetate (45 mg, 0.2 mmol) and tri-o-tolylphosphine (203 mg, 0.66 mmol). The mixture was placed in a pressure reactor under 50 psig of ethylene pressure and heated at 85C for 66 hours. The reaction mixture was cooled, vented, and partitioned between phosphate buffer (0.1 M, pH 6.6) and ethyl acetate. The aqueous phase was extracted with ethyl acetate twice more. The combined ethyl acetate extracts were washed with additional phosphate buffer, brine and dried over sodium sulfate. The extracts were filtered and evaporated to afford 2.06 g (63%) of the title product as a flaky crystalline residue. Recrystallization from ethyl acetate/cyclohexane gave colorless flakes. mp 120 - 121 C 1H NMR (CDCl3): delta = 8.55 (br, 1 H); 8.24 (d, 1 H); 8.15 (d, 1 H); 7.76 (d of d, 1H); 6.64 (d of d, 1 H); 5.73 (d, 1 H); 5.28 (d, 1 H); 2.19 (s, 3 H). MS (Cl): m/z= 163 (M+H+).
2.06 g (63%)	With triethylamine;palladium diacetate; In ethene; acetonitrile;	Preparation One N-(5-Vinyl-pyridin-2-yl)-acetamide. A solution of N-(5-bromo-pyridin-2-yl)-acetamide (4.30 g, 20 mmol) in acetonitrile (15 ml) and triethylamine (5.04 ml) was treated with palladium acetate (45 mg, 0.2 mmol) and tri-o-tolylphosphine (203 mg, 0.66 mmol). The mixture was placed in a pressure reactor under 50 psig of ethylene pressure and heated at 85C for 66 hours. The reaction mixture was cooled, vented, and partitioned between phosphate buffer (0.1 M, pH 6.6) and ethyl acetate. The aqueous phase was extracted with ethyl acetate twice more. The combined ethyl acetate extracts were washed with additional phosphate buffer, brine and dried over sodium sulfate. The extracts were filtered and evaporated to afford 2.06 g (63%) of the title product as a flaky crystalline residue. Recrystallization from ethyl acetate/cyclohexane gave colorless flakes. mp 120 - 121 C 1H NMR (CDCl3): delta = 8.55 (br, 1 H); 8.24 (d, 1 H); 8.15 (d, 1 H); 7.76 (d of d, 1H); 6.64 (d of d, 1 H); 5.73 (d, 1 H); 5.28 (d, 1 H); 2.19 (s, 3 H). MS (Cl): m/z= 163 (M+H+).

2.06 g (63%)	With triethylamine;palladium diacetate; In ethene; acetonitrile;	N-(5-Vinyl-pyridin-2-yl)-acetamide . A solution of of N-(5-bromo-pyridin-2-yl)-acetamide (prepared as described in Preparation One, 4.30 g, 20 mmol) in acetonitrile (15 ml) and triethylamine (5.04 ml) was treated with palladium acetate (45 mg, 0.2 mmol) and tri-o-tolylphosphine (203 mg, 0.66 mmol). The mixture was placed in a pressure reactor under 50 psig of ethylene pressure and heated at 85 C for 66 hours. The reaction mixture was cooled, vented, and partitioned between phosphate buffer (0.1 M, pH 6.6) and ethyl acetate. The aqueous phase was extracted with ethyl acetate twice more. The combined ethyl acetate extracts were washed with additional phosphate buffer, brine and dried over sodium sulfate. The extracts were filtered and evaporated to afford 2.06 g (63%) of the title product as a flaky crystalline residue. Recrystallization from ethyl acetate/cyclohexane gave colorless flakes. mp 120 - 121 C 1H NMR (CDCl3): delta = 8.55 (br, 1 H); 8.24 (d, 1 H); 8.15 (d, 1 H); 7.76 (d of d, 1 H); 6.64 (d of d, 1 H); 5.73 (d, 1 H); 5.28 (d, 1 H); 2.19 (s, 3 H). MS (Cl): m/z =163 (M+H+).
2.06 g (63%)	With triethylamine;palladium diacetate; In ethene; acetonitrile;	N-(5-Vinyl-pyridin-2-yl)-acetamide A solution of of N-(5-bromo-pyridin-2-yl)-acetamide (4.30 g, 20 mmol) in acetonitrile (15 ml) and triethylamine (5.04 ml) was treated with palladium acetate (45 mg, 0.2 mmol) and tri-o-tolylphosphine (203 mg, 0.66 mmol). The mixture was placed in a pressure reactor under 50 psig of ethylene pressure and heated at 85 C. for 66 hours. The reaction mixture was cooled, vented, and partitioned between phosphate buffer (0.1 M, pH 6.6) and ethyl acetate. The aqueous phase was extracted with ethyl acetate twice more. The combined ethyl acetate extracts were washed with additional phosphate buffer, brine and dried over sodium sulfate. The extracts were filtered and evaporated to afford 2.06 g (63%) of the title product as a flaky crystalline residue. Recrystallization from ethyl acetate/cyclohexane gave colorless flakes. mp 120-121 C. 1H NMR (CDCl3): delta=8.55 (br, 1 H); 8.24 (d, 1 H); 8.15 (d, 1 H); 7.76 (d of d, 1H); 6.64 (d of d, 1 H); 5.73 (d, 1 H); 5.28 (d, 1 H); 2.19 (s, 3 H). MS (Cl): m/z=163 (M+H+).

Reference： [1]Patent: US6657063,2003,B1 .Location in patent: Page column 92
[2]Patent: EP887079,1998,A1
[3]Patent: EP994105,2000,A2
[4]Patent: EP920864,1999,A1
[5]Patent: US6291489,2001,B1

3
[ 53910-10-4 ]
[ 374119-31-0 ]
[ 6163-58-2 ]
[ 374119-30-9 ]

Yield	Reaction Conditions	Operation in experiment
	With CuI; N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate; acetic acid; triethylamine; lithium chloride;palladium diacetate; In methanol; water; N,N-dimethyl-formamide;	(g) (S)-6-[1-carboxy-2-(3-methylphenyl)-ethylamino]-phthalide A solution of <strong>[53910-10-4]6-iodophthalide</strong> (1.0 g, 3.85 mmol), (S)-3-methylphenylalanine.HCl (0.83 g, 3.85 mmol) K2CO3 (0.53 g, 3.85 mmol), CuI (73 mg, 0.38 mmol), TEBA (0.32 g, 1.3 mmol), tri-o-tolylphosphine (0.23 g, 0.77 mmol), Pd(OAc)2 (86 mg, 0.38 mmol), triethylamine (2.14 mL, 15.38 mmol) and water (1.2 mL) in DMF (12 mL) is heated to 100 C. for 12 h. After cooling, the solution is diluted with EtOAc, and washed with 1 N HCl (100 mL), sat'd LiCl (50 mL) and water (100 mL), evaporated and chromatographed (2% MeOH/CH2Cl2, 0 to 0.05% acetic acid) to yield (S)-6-[(1-carboxy-2-(3-methylphenyl)-ethylamino]-phthalide, as a light brown foam. Other N-arylphenylalanines are similarly prepared.

Reference： [1]Patent: US2003/158256,2003,A1

4
[ 289039-82-3 ]
[ 56-37-1 ]
[ 6163-58-2 ]
silver carbonate [ No CAS ]
[ 397329-44-1 ]

Yield	Reaction Conditions	Operation in experiment
17%	With sodium bicarbonate;palladium diacetate; In water; N,N-dimethyl-formamide;	(202-2) Under nitrogen atmosphere, a suspension of <strong>[289039-82-3]methyl 5-chloro-2-iodobenzoate</strong> (Example 109-9) (220 mg), the compound of Example 202-1 (200 mg), Pd(OAc)2 (22.9 mg), BnEt3NCl (171 mg), sodium hydrogen carbonate (130 mg), tri-o-tolylphosphine (68.4 mg) in DMF (4.0 mL) was stirred at 80 C. for 4 hours, and stirred at 100 C. for 11 hours, during which silver (I) carbonate (207 mg) was added thereto. The mixture was cooled to room temperature, and the mixture was filtered. Water was added to the filtrate, and the mixture was extracted with ethyl acetate/toluene. The organic layer was washed with water and a saturated brine, and dried over MgSO4. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column (hexane/ethyl acetate=7/1?5/1) to give methyl 5-chloro-2-{(1E)-4-[2-(4-methoxybenzoyl)-4-methyl-1H-pyrrol-1-yl]-1-butenyl}benzoate (55.0 mg, 17%). 1H NMR (CDCl3, 400 MHz) delta 7.81 (d, 1H, J=2.2 Hz), 7.77 (d, 2H, J=8.8 Hz), 7.36 (d, 1H, J=8.5 Hz), 7.32 (dd, 1H, J=2.2, 8.5 Hz), 7.10 (d, 1H, J=15.7 Hz), 6.90 (d, 2H, J=8.8 Hz), 6.77 (d, 1H, J=1.4 Hz), 6.51 (d, 1H, J=1.4 Hz), 6.08 (dt, 1H, J=15.7, 7.1 Hz), 4.49 (t, 2H, J=7.1 Hz), 3.89 (s, 3H), 3.87 (s, 3H), 2.72 (dt, 2H, J=7.1, 7.1 Hz), 2.07 (s, 3H).

Reference： [1]Patent: US2003/181496,2003,A1

5
[ 100-43-6 ]
[ 130284-53-6 ]
[ 6163-58-2 ]
[ 552330-65-1 ]

Yield	Reaction Conditions	Operation in experiment
84%	With triethylamine;tris-(dibenzylideneacetone)dipalladium(0); In ethyl acetate; N,N-dimethyl-formamide;	Example 21A 6-chloro-5-[(E)-2-pyridin-4-ylvinyl]pyridin-3-amine A solution of <strong>[130284-53-6]3-amino-5-bromo-6-chloropyridine</strong> (2.0 g, 9.64 mmol), Pd2(dba)3 (440 mg, 0.48 mmol), tri-o-tolylphosphine (438 mg, 1.44 mmol), 4-vinylpyridine (2.08 mL, 19.28 mmol), and triethylamine (4.03 mL, 29 mmol) in DMF (30 mL) was stirred at 100 C. for 15 hours, cooled to room temperature, treated with ethyl acetate (200 mL), washed twice with brine, dried (MgSO4), filtered and concentrated. The residual solid recrystallized from hexanes/dichloromethane to provide desired product (1.86 g, 84%). MS (APCI) m/e 232 (M+H)+.

Reference： [1]Patent: US2003/187026,2003,A1

6
tert-butyl (1R)-1-[2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxa-borolan-2-yl)phenyl]ethylcarbonate [ No CAS ]
[ 685892-23-3 ]
[ 6163-58-2 ]
[ 1048975-24-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;palladium diacetate; In tetrahydrofuran; water; ethyl acetate;	A mixture of <strong>[685892-23-3]methyl 2-bromo-6-chlorobenzoate</strong> (2.25 g, 9.03 mmol), tert-butyl (1R)-1-[2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-ethylcarbonate (see Example 11, 3.00 g, 8.21 mmol), potassium carbonate (2.84 g, 20.5 mmol), tri-o-tolylphosphine (0.10 g, 0.33 mmol), and palladium acetate (0.018 g, 0.08 mmol) in 40 mL of THF and 4 mL of water was heated in a sealed flask at 100 C. for 4 h. The mixture was then cooled and concentrated in vacuo. The resulting residue was dissolved in ethyl acetate, washed with water and brine, dried over Na2SO4, filtered and concentrated under vacuum. The residue was subjected to silica gel chromatography eluted with 0-10% ethyl acetate and hexane to provide methyl 4'-{(1R)-1-[(tert-butoxycarbonyl)amino]ethyl}-3-chloro-3'-fluoro-1,1'-biphenyl-2-carboxylate that gave proton NMR spectra consistent with theory.

Reference： [1]Patent: US2003/220375,2003,A1

7
[ 101935-40-4 ]
[ 6163-58-2 ]
[ 140-88-5 ]
[ 153136-82-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	With triethylamine;palladium diacetate;	Example 206 Ethyl (2E)-3-(2-hydroxy-6-nitrophenyl)prop-2-enoate To a thick-walled vessel was charged with <strong>[101935-40-4]2-bromo-3-nitrophenol</strong> (1.16 g, 5.32 mmol), ethyl acrylate (666 mg, 0.72 mmol), tri-(o-tolyl)phosphine (65 mg, 0.21 mmol), palladium acetate (12 mg, 0.05 mmol), and triethylamine(10 mL). The vessel was then sealed and the resulting mixture was heated to 100 C. overnight. In the morning, the vessel was cooled to rt and the mixture was poured into water. The mixture was acidified with hydrochloric acid and extracted with ethyl acetate (2*50 mL). The combined organic layer was washed with water, brine and dried over anhydrous sodium sulfate. The residue was purified with silica gel flash chromatography by using hexane/ethyl acetate (2/1) as the eluant to give ethyl (2E)-3-(2-hydroxy-6-nitrophenyl)prop-2-enoate (883 mg, 70%): Rf 0.16 (3/1 hexane/ethyl acetate); 1H NMR (CDCl3) delta7.6(d, J=16.1 Hz, 1H), 7.05-7.23 (m, 3H), 6.71 (dd, J=16.1, 0.8 Hz, 1H), 4.18 (q, J=7.1 Hz, 2H), 1.26 (t, J=7.1 Hz, 2H).

Reference： [1]Patent: US2003/87902,2003,A1

8
[ 1075-34-9 ]
[ 292638-85-8 ]
[ 6163-58-2 ]
[ 546114-96-9 ]

Yield	Reaction Conditions	Operation in experiment
73%	With triethylamine;palladium diacetate;	3-(2-Methylindol-5-yl)acrylic Acid Methyl Ester A mixture of <strong>[1075-34-9]5-bromo-2-methylindole</strong> (2.10 g, 10.0 mmol), methyl acrylate (1.08 g, 12.5 mmol), palladium acetate (23.2 mg, 0.1 mmol), tri(o-tolyl)phosphine (61.3 g, 0.2 mmol) and triethylamine (3.62 g, 35.8 mmol) was heated under argon in a heavy-walled Pyrex tube at 100° C. for 3 h. The cooled reaction mixture was diluted with DCM (60 mL) and distilled water (30 mL). The organic layer was washed with distilled water (3*25 mL). The aqueous is layer was extracted with DCM (25 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give a pale yellow solid. Purification by recrystallization with EtOAc gave a pale yellow powder (1.57 g; 73percent): mp 172-173° C.; Rf0.35 (C); Rf0.61 (E); numax (KBr): 3295, 1698, 1305, 1282, 1165, 975 cm-1; m/z (EI): 215.1, 184.1, 156.1, 77.2; deltaH (CDCl3, 400 MHz): 2.45 (3 H, s), 3.82 (3 H, s), 6.25 (1 H, s), 6.42 (1 H, d, J=16.0), 7.27 (1 H, d, J=8.0), 7.35 (1 H, d, J=8.0), 7.69 (1 H, s), 7.85 (1 H, d, J=16.0), 8.15 (1 H, bs); deltaC (CDCl3, 101 MHz): 14.0, 51.8, 101.5, 111.0, 114.5, 121.1, 121.4, 126.5, 129.7, 136.7, 137.7, 147.4, 168.6; m/z calculated for C13H13NO2: 215.0946 (M+), found 215.0945 (M+).

Reference： [1]Patent: US2003/114441,2003,A1

9
[ 17117-17-8 ]
[ 252870-83-0 ]
[ 6163-58-2 ]
[ 252871-06-0 ]

Yield	Reaction Conditions	Operation in experiment
0.67 g (35.2%)	With triethylamine;palladium diacetate; In acetonitrile;	(4E)-N-Methyl-N-(tert-butoxycarbonyl)-5-(5-ethoxy-3-pyridyl)-4-penten-2-amine Under a nitrogen atmosphere, a mixture of <strong>[17117-17-8]5-ethoxy-3-bromopyridine</strong> (1.20 g, 5.94 mmol), N-methyl-N-(tert-butoxycarbonyl)-4-penten-2-amine (1.18 g, 5.94 mmol), palladium(II) acetate (13.5 mg, 0.06 mmol), tri-o-tolylphosphine (73.1 mg, 0.24 mmol), triethylamine (1.5 mL, 10.8 mmol), and anhydrous acetonitrile (3 mL) was stirred and heated under reflux at 80-85 C. for 28 h. The resulting mixture, containing beige solids, was cooled to ambient temperature, diluted with water (20 mL), and extracted with CHCl3 (3*20 mL). The combined light-yellow CHCl3 extracts were dried (Na2SO4), filtered, concentrated by rotary evaporation, and vacuum dried producing a yellow oil (1.69 g). The crude product was purified by column chromatography on silica gel (100 g), eluding with ethyl acetate-hexane (1:1, v/v). Selected fractions containing the product (Rf 0.20) were combined, concentrated by rotary evaporation, and the residue was vacuum dried to give 0.67 g (35.2%) of a light-yellow oil.

Reference： [1]Patent: US2003/125345,2003,A1

10
(OAc)2 [ No CAS ]
[ 436150-25-3 ]
[ 98546-51-1 ]
[ 6163-58-2 ]
[ 128312-11-8 ]
9,9,9-trifluoro-N-(4'-(methylsulfanyl)(1,1'-biphenyl)-3-yl)-8-oxononanamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
164 mg (48%)	With sodium carbonate;palladium diacetate; In 1,2-dimethoxyethane;	Example 54B 9,9,9-trifluoro-N-(4'-(methylsulfanyl)(1,1'-biphenyl)-3-yl)-8-oxononanamide A mixture of Example 54A (308 mg, 0.81 mmol), 4-(methylsulfanyl)phenyl-boronic acid (150 mg, 0.89 mmol), Pd(OAc)2 (9.1 mg, 0.04 mmol), tri-o-tolylphosphine (24.4 mg, 0.08 mmol), and 2M Na2CO3 (2 mL, 2 mmol) in DME (5 mL) was heated to 80 C. for 3 hours, treated with additional Pd (OAc)2 (9 mg), tri-o-tolylphosphine (24 mg), and <strong>[128312-11-8]3-(methylsulfanyl)phenyl-boronic acid</strong> (75 mg), heated for 3 hours, cooled to room temperature, and partitioned between diethyl ether and water. The aqueous phase was extracted with diethyl ether and the combined extracts were washed with brine, dried (Na2SO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 7:3 hexanes/ethyl acetate to provide 164 mg (48%) of the desired product. MS (ESI(-)) m/e 422 (M-H)-; 1H NMR (300 MHz, DMSO-d6) delta9.94 (s, 1H), 7.90 (s, 1H), 7.55 (d, 3H), 7.42-7.22 (m, 4H), 2.86 (t, 2H), 2.49 (s, 3H), 2.33 (t, 2H), 1.68-1.51 (m, 4H), 1.36-1.27 (m, 4H); Anal. Calcd for C22H24NO2F3S: C, 62.39; H, 5.71; N, 3.31. Found: C, 63.18; H, 5.60; N, 2.75.
164 mg (48%)	With sodium carbonate;palladium diacetate; In 1,2-dimethoxyethane;	Example 54B 9,9,9-trifluoro-N-(4 '-(methylsulfanyl)(1,1'-biphenyl)-3-yl)-8-oxononanamide A mixture of Example 54A (308 mg, 0.81 mmol), 4-(methylsulfanyl)phenyl-boronic acid (150 mg, 0.89 mmol), Pd(OAc)2 (9.1 mg, 0.04 mmol), tri-o-tolylphosphine (24.4 mg, 0.08 mmol), and 2M Na2CO3 (2 mL, 2 mmol) in DME (5 mL) was heated to 80 C. for 3 hours, treated with additional Pd (OAc)2 (9 mg), tri-o-tolylphosphine (24 mg), and <strong>[128312-11-8]3-(methylsulfanyl)phenyl-boronic acid</strong> (75 mg), heated for 3 hours, cooled to room temperature, and partitioned between diethyl ether and water. The aqueous phase was extracted with diethyl ether and the combined extracts were washed with brine, dried (Na2SO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 7:3 hexanes/ethyl acetate to provide 164 mg (48%) of the desired product. MS (ESI(-)) m/e 422 (M-H)-; 1H NMR (300 MHz, DMSO-d6) delta 9.94 (s, 1H), 7.90 (s, 1H), 7.55 (d, 3H), 7.42-7.22 (m, 4H), 2.86 (t, 2H), 2.49 (s, 3H), 2.33 (t, 2H), 1.68-1.51 (m, 4H), 1.36-1.27 (m, 4H); Anal. Calcd for C22H24NO2F3S: C, 62.39; H, 5.71; N, 3.31. Found: C, 63.18; H, 5.60; N, 2.75.

Reference： [1]Patent: US2002/177594,2002,A1
[2]Patent: US2002/103192,2002,A1

11
[ 60633-25-2 ]
[ 6163-58-2 ]
[ 140-88-5 ]
[ 105475-30-7 ]

Yield	Reaction Conditions	Operation in experiment
	palladium diacetate; In n-heptane; triethylamine;	a Ethyl 5-chloro-2-methoxycinnamate A solution of 10.6 g (48.2 mmol) of <strong>[60633-25-2]2-bromo-4-chloroanisole</strong> in 30 ml of triethylamine was treated with 1 0.1 ml (81.2 mmol) of ethyl acrylate, 1.23 g of tri-o-tolylphosphine, and 0.45 g of palladium(II) acetate in an argon atmosphere. The reaction mixture was stirred at 100 C. for 2 days, then diluted with EA and filtered through Celite. The filtrate was washed with 1 N HCl and saturated NaCl solution, dried over Na2SO4, and concentrated. After chromatographic purification over SiO2 using EA/heptane (1:8) as an eluent, 0.85 g of the title compound resulted as a pale yellow oil. Rf (SiO2, EA/heptane 1:4)=0.34. MS (ESI): m/e=241 (M+H)+

Reference： [1]Patent: US6350778,2002,B1

12
[ 17117-17-8 ]
[ 813-19-4 ]
[ 6163-58-2 ]
[ 227306-34-5 ]

Yield	Reaction Conditions	Operation in experiment
32%	With triethylamine;palladium diacetate; In acetonitrile; pentane;	PREPARATION 169 3-Ethoxy-5-(tri-n-butylstannyl)pyridine A stirred mixture of <strong>[17117-17-8]3-bromo-5-ethoxypyridine</strong> (Rec. Trav. chim., 1948, 67, 377; 930 mg, 4.6 mmol), bis(tri-n-butyltin) (3.46 ml, 6.9 mmol), tri-o-tolylphosphine (420 mg, 1.37 mmol), palladium(II) acetate (78 mg, 0.35 mmol), triethylamine (1.23 ml, 8.84 mmol) and acetonitrile (15 ml), under nitrogen, was heated under reflux for 18 hours, then allowed to cool. The solution was decanted from the black, tarry residue and evaporated under reduced pressure, then the resulting residue flash chromatographed, using an elution gradient of ethyl acetate:pentane (0:100 to 5:95), to yield the title compound (600 mg, 32%) as a colourless oil. delta(CDCl3): 0.90 (t,9H), 1.08 (t,6H), 1.30-1.42 (m,6H), 1.42 (t,3H), 1.58 (m,6H), 4.08 (q,2H), 7.25 (s,1H), 8.17 (s,1H), 8.19 (s,1H).

Reference： [1]Patent: US6387931,2002,B1

13
[ 27325-97-9 ]
[ 26163-03-1 ]
[ 6163-58-2 ]
[ 301542-49-4 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In N,N-dimethyl-formamide;	Preparation 10 (E)-2-(2-Amino-5-chloro-3-pyridinyl)-N-methyl-1-ethenesulphonamide A mixture of <strong>[26163-03-1]3-bromo-5-chloro-2-pyridinamine</strong> (414 mg, 2 mmol), N-methyl ethene sulphonamide (266 mg, 2.2 mmol) and triethylamine (555 mul, 4 mmol), palladium acetate (18 mg, 0.08 mmol) and tri-o-tolylphosphine (50 mg, 0.16 mmol) in DMF (0.5 ml) in a Teflon.(TM). pressure vessel was microwaved for 30 sec (full power), allowed to cool to RT and irradiated for a further 30 sec. After allowing to cool, the reaction mixture was diluted with water, extracted with EtOAc and the organic phase washed with saturated brine, dried over MgSO4, and concentrated to a brown semi-solid. Purification by column chromatography on silica gel eluding with methylene chloride-methanol (95:5), and then crystallisation from methanol gave the title compound (130 mg, 0.5 mmol): 1H (delta, d6-DMSO, 400 MHz) 2.5 (3H, s), 6.5 (2H, br s), 6.95 (1H, br s), 7.1 (1H, d), 7.35 (1H, d), 7.95 (1H, s), 8.0 (1H, s); LRMS 248, 250 (MH); M. Pt. 194-8° C.; El. Anal.-Found: C, 38.61; H, 4.04; N, 16.61. Calcd for C8H10ClNO2S: C, 38.79; H, 4.07; N, 16.97.

Reference： [1]Patent: US6583162,2003,B1

14
hexane-EtOAc [ No CAS ]
[ 1663-39-4 ]
[ 26163-03-1 ]
[ 6163-58-2 ]
[ 301542-40-5 ]

Yield	Reaction Conditions	Operation in experiment
	palladium diacetate; In triethylamine;	Preparation 1 t-Butyl (E)-3-(2-amino-5-chloro-3-pyridinyl)-2-propenoate A mixture of <strong>[26163-03-1]3-bromo-5-chloro-2-pyridinamine</strong> (C. W. Murtiashaw, R. Breitenbach, S. W. Goldstein, S. L. Pezzullo, J. Quallich, R. Sarges, J. Org. Chem., 1992, 57, 1930) (8.56 g, 41.4 mmol), t-butyl acrylate (12 ml, 82 mmol), tri-o-tolylphosphine (2.92 g. 9.6 mmol) and palladium acetate (540 mg, 2.4 mmol) in triethylamine (130 ml) was heated in a sealed bomb to 150° C. for 10 hours. The reaction mixture was filtered, the residue washed with EtOAc and the combined filtrates evaporated to a dark brown oil. Purification by column chromatography upon silica gel using hexane-EtOAc (7:3) as eluant and subsequent crystallisation from hexane at -78° C. gave the title compound as a bright yellow solid (4.75 g, 18.6 mmol). 1H (delta, CDCl3, 300 MHz) 1.5 (9H, s), 4.7 (2H, br s), 6.3 (1H, d), 7.45 (1H, d), 7.55 (1H, s), 8.0 (1H, s); LRMS 255, 257 (MH); El. Anal.-Found: C, 56.55; H, 5.94; N, 10.91. Calcd for C12H15ClN2O2: C, 56.58; H, 5.94; N, 10.99.

Reference： [1]Patent: US6583162,2003,B1

15
[ 26163-03-1 ]
[ 6163-58-2 ]
[(E)-2-(1,3-benzodioxol-5-yl)ethenyl]tributylstannane [ No CAS ]
[ 301542-55-2 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In N,N-dimethyl-formamide;	Preparation 16 3-[(E)-2-(1,3-Benzodioxol-5-yl)ethenyl]-5-chloro-2-pyridinamine A solution of <strong>[26163-03-1]3-bromo-5-chloro-2-pyridinamine</strong> (318 mg, 1.5 mmol), [(E)-2-(1,3-benzodioxol-5-yl)ethenyl](tributyl)stannane (250 mg, 1.7 mmol) (A. J. Bridges, A. Lee, C. E. Schwatrz, M. J. Towle, B. A. Littlefield, Bioorg. Med. Chem., 1993, 1, 403), palladium acetate (19 mg, 0.08 mmol) and tri-o-tolylphosphine (50 mg, 0.16 mmol) in DMF (0.5 ml) and triethylamine (0.5 ml) in a teflon pressure vessel was heated in a microwave (full power) for 20 sec, allowed to cool to RT heated in a microwave for a further 20 sec and then 1 min 20 sec. After allowing to cool, the reaction mixture was poured into water (20 ml) and extracted with EtOAc (320 ml). The combined extracts were washed with water (220 ml), dried over MgSO4 and concentrated. Recrystallisation from EtOAc-hexane gave the title compound as a brown solid (170 mg, 0.6 mmol): 1 H (delta, CDCl3, 300 MHz) 4.55 (2H, br s), 6.0 (2H, s), 6.7 (1 H, d), 6.8 (1H, d), 6.9-7.0 (2H, m), 7.05 (1H, s), 7.55 (1H, s), 7.95 (1H, s); LRMS 275, 277 (MH).

Reference： [1]Patent: US6583162,2003,B1

16
[ 52409-22-0 ]
[ 22282-75-3 ]
[ 6163-58-2 ]
[ 203520-03-0 ]
[ 211820-04-1 ]

Yield	Reaction Conditions	Operation in experiment
	In 1,4-dioxane; dichloromethane;	To a suspension of <strong>[22282-75-3]3-fluoro-4-iodopyridine</strong> (2.23 g), 1-(tert-butoxycarbonyl)-4-(piperidin-4-ylcarbonyl)piperazine (1.49 g) and sodium t-butoxide (1.06 g) in 1,4-dioxan (20 ml) was added tris(dibenzylidene acetone)dipalladium(0) (0.09 g) and tri-o-tolylphosphine (0.12 g) and the mixture heated at reflux for 3 hours. The mixture was diluted with diethyl ether and washed with saturated aqueous sodium chloride solution, dried (Na2SO4) and evaporated. The residue was purified by chromatography on alumina (N32-63) eluding with 0.4percent methanol in dichloromethane to give as a solid, 1-(tert-butoxycarbonyl)-4-[1-(3-fluoro-4-pyridyl)piperidin-4-ylcarbonyl]piperazine (0.70 g). 1H-NMR (CDCl3): 1.45 (s, 9H), 1.80 (m, 2H), 2.00 (m, 2H), 2.65 (m, 1H), 2.90 (m, 2H), 3.40 (m, 8H), 3.80 (m, 2H), 6.70 (dd, 1H), 8.10 (d, 1H) and 8.20 (d, 1H); m/z 393 (M+1).
	In 1,4-dioxane; dichloromethane;	To a suspension of <strong>[22282-75-3]3-fluoro-4-iodopyridine</strong> (2.23 g), 1-(tert-butoxycarbonyl)-4-(piperidin-4-ylcarbonyl) piperazine (1.49 g) and sodium t-butoxide (1.06 g) in 1,4-dioxan (20 ml) was added tris(dibenzylidene acetone)dipalladium(0) (0.09 g) and tri-o-tolylphosphine (0.12 g) and the mixture heated at reflux for 3 hours. The mixture was diluted with diethyl ether and washed with saturated aqueous sodium chloride solution. dried (Na2SO4) and evaporated. The residue was purified by chromatography on alumina (N32-63) eluding with 0.4percent methanol in dichloromethane to give as a solid, 1-(tert-butoxycarbonyl)-4-[1-(3-fluoro-4-pyridyl)piperidin-4-ylcarbonyl]piperazine (0.70 g). 1H-NMR (CDCl3): 1.45 (s, 9H), 1.80 (m, 2H), 2.00 (m, 2H), 2.65 (m, 1H), 2.90 (m, 2H), 3.40 (m, 8H), 3.80 (m, 2H), 6.70 (dd, 1H), 8.10 (d, 1H) and 8.20 (d, 1H); m/z 393 (M+1).

Reference： [1]Patent: US6440972,2002,B1
[2]Patent: US6440972,2002,B1

17
[ 827-54-3 ]
[ 53087-78-8 ]
[ 6163-58-2 ]
Ethyl 2-(2-naphthylethen-1-yl)pyridine-3-carboxylate Hydrochloride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; triethylamine;palladium diacetate; In 1,4-dioxane; N-methyl-acetamide; water; acetone;	a Ethyl 2-(2-naphthylethen-1-yl)pyridine-3-carboxylate Hydrochloride 10 g (43.5 mmol) of <strong>[53087-78-8]ethyl 2-bromopyridine-3-carboxylate</strong>, 8.7 g (56.5 mmol) of 2-vinylnaphthalene, 15 ml (0.11 mol) of triethylamine, 0.36 g of palladium(II) acetate and 0.96 g of tri-o-tolylphosphine were dissolved in 150 ml of dimethylformamide. A further 1 ml of water was then added and the entire mixture was refluxed for 3 h. The entire mixture was then extracted with ether. The organic phase was additionally washed with water, dried and concentrated in vacuo. The residue was dissolved in acetone and treated with hydrogen chloride, dissolved in dioxane. The product was then precipitated by addition of ether. 8.7 g (67%) of the product were obtained.

Reference： [1]Patent: US6630493,2003,B1

18
[ 203520-35-8 ]
[ 22282-75-3 ]
[ 6163-58-2 ]
[ 211820-06-3 ]

Yield	Reaction Conditions	Operation in experiment
	tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; methanol; dichloromethane;	Tris(dibenzylideneacetone)dipalladium(0) (0.184 g) and tri-o-tolylphosphine (0.244 g) were added to a suspension of <strong>[22282-75-3]3-fluoro-4-iodopyridine</strong> (4.46 g), 1-[1-(t-butoxycarbonyl)piperazin-4-ylcarbonyl]piperazine (3.0 g) and sodium t-butoxide (2.12 g) in dry 1,4-dioxane (40 ml) under an atmosphere of argon. The mixture was heated at 100° C. for 18 hours. The mixture was cooled, diluted with diethyl ether (200 ml) and washed with saturated brine (40 ml). The aqueous layer was back-extracted with diethyl ether (2100 ml). The ether layers were all combined, washed with saturated brine (2100 ml), dried (Na2SO4) and evaporated. The residual oil was purified by chromatography on alumina (N32-63) using 0.1-0.4percent methanol in dichloromethane as eluent to give 1-(t-butoxycarbonyl)-4-[1-(3-fluoro-4-pyridyl)piperazin-4-ylcarbonyl]piperazine (1.7 g) as an orange solid: NMR (CDCl3): 1.47 (s, 9H), 3.25 (m, 8H), 3.45 (m, 8H), 6.75 (dd, 1H), 8.20 (dd, 2H); m/z 394 (M+1).

Reference： [1]Patent: US6440972,2002,B1

19
[ 261732-38-1 ]
[ 623-70-1 ]
[ 6163-58-2 ]
petrol [ No CAS ]
[ 261732-36-9 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In N-methyl-acetamide; ethyl acetate;	(a) Ethyl 3-(1-boc-2,3-Dihydro-1H-indol-5-yl)crotonate A mixture of 1-boc-5-bromoindoline (15.0 g, Reference Example 8), ethyl crotonate (8.6 g), palladium acetate (480 mg), tris(o-tolyl)phosphine (1.6 g) and triethylamine (10 ml) in dimethylformamide (60 ml) was stirred in a sealed vessel under an atmosphere of argon at about 100 C. for about 4 hours. After cooling to room temperature the dark mass was poured onto hydrochloric acid (about 1 L, 1M) and the product extracted into ethyl acetate. The combined extracts were washed with aqueous sodium bicarbonate solution, then with brine, then dried and then evaporated. The residual light yellow oil was subjected to flash chromatography on silica eluding initially with a mixture of ethyl acetate and petrol (5:95, v/v) to remove high running impurities, then eluding with a mixture of ethyl acetate and petrol (1:9, v/v) to give the title compound (11.4 g) as a colourless, mobile oil.

Reference： [1]Patent: US6608084,2003,B1

20
NaOBut [ No CAS ]
[ 2398-37-0 ]
[ 109-07-9 ]
[ 6163-58-2 ]
[ 83949-40-0 ]

Yield	Reaction Conditions	Operation in experiment
	tris-(dibenzylideneacetone)dipalladium(0); In o-xylene; water;	Comparative Example 7 A 100 ml Kjeldahl flask equipped with a cooling condenser and a thermometer was charged with 96 mg of tris(dibenzylideneacetone)dipalladium (supplied by Aldrich) and 10 ml of o-xylene at room temperature in a nitrogen atmosphere. 257 mg of tri-o-tolylphosphine was added to the content in the flask while being stirred, and maintained at 60 C. for 10 minutes with stirring in an oil, to give a catalyst. The content was then cooled to room temperature, and, in a nitrogen atmosphere, 1.36 g of 2-methylpiperazine, 2.0 g of m-bromoanisole as an aryl halide (the ratio of palladium atom/aryl halide=2.0% by mole) and 1.43 g of NaOBut were separately incorporated into the flask, each as a solution in 10 ml of o-xylene. The content in the flask was to 100 C. and maintained at that temperature for 3 hours with stirring. After completion of the reaction, the content was concentrated, water was added to the residue, and then, the mixture was extracted with ethyl acetate. The liquid extract was concentrated and dried in vacuum overnight to give brown oily N-(3-methoxyphenyl)-2-methylpiperazine. The result of the gas chromatographic analysis of the product is shown in Table 2.

Reference： [1]Patent: US5929281,1999,A

21
[ 180307-56-6 ]
{4-[6-bromo-1-(4-fluoro-benzyl)-1H-indazol-3-yl]-piperidin-1-yl}-acetic acid tert-butyl ester [ No CAS ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 180307-57-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate; triethylamine; lithium chloride; In N,N-dimethyl-formamide;	(x) 4-{2-[3-(1-tert-Butoxycarbonylmethyl-piperidin-4-yl)-1-(4-fluoro-benzyl)-1H-indazol-6-yl]-(E)-vinyl}-piperidine-1-carboxylic acid tert-butyl ester A stirred mixture of {4-[6-bromo-1-(4-fluoro-benzyl)-1H-indazol-3-yl]-piperidin-1-yl}-acetic acid tert-butyl ester (286 mg, 0.57 mmol), <strong>[180307-56-6]4-vinyl-piperidine-1-carboxylic acid tert-butyl ester</strong> (120 mg, 0.57 mmol), lithium chloride (24 mg, 0.57 mmol), triethylamine (0.24 ml, 1.71 mmol), palladium (II) acetate (8 mg 0.03 mmol), tri-o-tolylphosphine (35 mg, 0.11 mmol), and DMF (5 ml) was heated at 105 (oil-bath temperature) under nitrogen for 18 h. When cool, the mixture was evaporated in vacuo, treated with aqueous saturated sodium bicarbonate (20 ml), and extracted with ethyl acetate (2*20 ml). The combined, dried (Na2 SO4) organic extracts were evaporated, and the residue purified by flash chromatography over silica gel (Merck 9385). Elution with ethyl acetate --cyclohexane (1:2) afforded impure fractions and pure fractions (I). The impure fractions were purified by flash chromatography over silica gel (Merck-9385) eluding with ethyl acetate--cyclohexane (gradient 1:4 to 1:2) to give pure fractions (II). The pure fractions (I) and (II) were combined to give the title compound as a pale yellow oil (195 mg).

Reference： [1]Patent: US5861414,1999,A

22
[ 292638-85-8 ]
[ 6163-58-2 ]
[ 57946-63-1 ]
[ 231296-98-3 ]

Yield	Reaction Conditions	Operation in experiment
1.65 g (80.8%)	With triethylamine;palladium diacetate; In ethyl acetate; acetonitrile;	Step 1. Methyl trans-2-amino-5-(trifluoromethyl)cinnamate A mixture of <strong>[57946-63-1]4-amino-3-bromobenzotrifluoride</strong> (2.0 g, 8.33 mmol), methyl acrylate (1.9 ml, 20.83 mmol), palladium acetate (224 mg, 1.00 mmol), tri-o-tolylphosphine (1.2 g, 4.00 mmol), triethylamine (4.5 ml) in acetonitrile (17 ml) were stirred at reflux temperature. After 2 h, methyl acrylate (1.0 ml, 10.41 mmol), palladium acetate (112 mg, 0.5 mmol), tri-o-tolylphosphine (0.6 g, 2.00 mmol) and triethylamine (2.3 ml) were added, and the mixture was stirred at reflux temperature for an additional 5 h. The mixture was concentrated and the residue was diluted in ethyl acetate. After washing with water the organic layer was dried (MgSO4), and concentrated. Purification by flash column chromatography eluding with hexane/ethyl acetate (gradient elution from 5:1 to 3:1) to afford 1.65 g (80.8percent) of the title compound as yellow crystals. 1H-NMR (CDCl3) delta: 7.77 (1H, d, J=15.8 Hz), 7.61 (1H, s), 7.39 (1H, d, J=8.4 Hz), 6.74 (1H, d, J=8.4 Hz), 6.41 (1H, dd, J=15.8, 1.5 Hz), 4.29 (2H, m), 3.82 (3H, m).

Reference： [1]Patent: US6303628,2001,B1

23
[ 186497-45-0 ]
[ 6163-58-2 ]
[ 182281-01-2 ]
[ 186497-59-6 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium fluoride;palladium diacetate; In water; ethyl acetate; toluene;	(iii) A solution of potassium fluoride (6.5 g) in water (100 ml) was added to a solution of 2-chloro-N-isobutoxycarbonyl-N-(3-methoxy-5-methylpyrazin-2-yl)pyridine-3-sulphonamide (7.8 g), 4-(2-(2 H)-tetrahydropyranyloxy)phenylboronic acid (10.0 g), tri-o-tolyl phosphine (0.73 g) and palladium acetate (0.25 g) in toluene (100 ml) and the mixture was heated under reflux under argon for 18 hours. Ethyl acetate (150 ml) was added and the organic phase was separated. The solution was washed with 2M sodium hydroxide solution (100 ml) and water (250 ml) and then dried (MgSO4). Volatile material was removed by evaporation and the residue was purified by flash chromatography, eluding with 25-50% ethyl acetatelhexane. The residue was crystallized from ethyl acetate/hexane to give N-(isobutoxycarbonyl)-2-[4-(2H-tetrahydropyran-2-yloxy)phenyl]-N-(3-methoxy-5-methylpyrazin-2-yl)pyridine-3-sulphonamide (4.0 g), m.p. 142-144 C.

Reference： [1]Patent: US5866568,1999,A

24
[ 2725-82-8 ]
[ 6163-58-2 ]
[ 57260-71-6 ]
[ 220996-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With nitrogen;palladium dichloride; In toluene;	Step 1. Into a 15 mL round-bottomed flask fitted with a reflux condensor, a magnetic stirring bar, and a nitrogen inlet was added 1 mL dry toluene followed by 0.016 g (0.09 mmol) PdCl2 and 0.055 g (0.18 mmol) tri-o-tolylphosphine. After stirring for 15 min, an additional 15 mL dry toluene was added followed by 0.33 g (1.8 mmol) <strong>[2725-82-8]3-ethylbromobenzene</strong>, 0.41 g (2.2 mmol) 1-Boc-piperazine and 0.242 g (2.5 mmol) sodium t-butoxide. The reaction was heated to reflux for 18 hr, after which time TLC (20% EtOAc/Hexane) showed the formation of a new spot. The reaction was cooled, diluted with 50 mL of ether, filtered through a Celite pad, and extracted with 310 mL water and 115 mL brine. The organic phase was dried (Na2SO4), filtered and the solvent removed in vacuo to get the crude product, which was purified by passing through a 2" silica pad (1% to 4% EtOAc/Hexane) to yield 1-Boc-4-(3-ethylphenyl)piperazine.

Reference： [1]Patent: US5968938,1999,A

25
[ 3034-22-8 ]
2-(R)-(1-(S)-(3,5-bis(trifluoromethyl)-phenyl)-2-hydroxyethoxy)-3-(S)-(4-fluorophenyl)morpholine [ No CAS ]
tris(dibenzylideneacetone)dipalladium ⁽⁰⁾ [ No CAS ]
[ 6163-58-2 ]
2-(R)-(1-(S)-(3,5-bis(trifluoromethyl)phenyl)-2-hydroxyethoxy)-4-(2-amino-5-thiazolyl)-3-(S)-(4-fluorophenyl)morpholine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With ammonia; sodium t-butanolate; In 1,4-dioxane; methanol; dichloromethane;	EXAMPLE 4 2-(R)-(1-(S)-(3,5-Bis(trifluoromethyl)phenyl)-2-hydroxyethoxy)-4-(2-amino-5-thiazolyl)-3-(S)-(4-fluorophenyl)morpholine To a degassed solution of 2-(R)-(1-(S)-(3,5-bis(trifluoromethyl) -phenyl)-2-hydroxyethoxy)-3-(S)-(4-fluorophenyl)morpholine (0.2 g), 2-amino-5-bromothiazole (0.14 g), sodium tert-butoxide (0.0105 g) and tri-o-tolylphosphine (0.007 g) in dioxane (4 ml) was added tris(dibenzylideneacetone)dipalladium (0) (0.02 g). The solution was degassed and then heated at 80° C. for 24 h under an atmosphere of nitrogen. The solvent was removed in vacuo and the residue partitioned between ethyl acetate and water. The organic layer was dried (MgSO4) and after evaporation of the solvent the residue was chromatographed on silica (eluding with gradient of 2percent -4percent methanol/ammonia (100:3) in dichloromethane) to give the title compound. 1 H NMR (360 MHz, CDCl3) delta3.11 (1H, td, J=11.7 Hz, 3.5 Hz), 3.19 (1H, bd J=11.4 Hz), 3.61 (1H, dd, J=12.2 Hz and 3.3 Hz), 3.67-3.81 (3H, m), 4.47 (1H, d, J=2.8 Hz), 4.54 (1H, td, J=11.7 Hz and 2.8 Hz), 4.80 (2H, bs), 4.92 (1H, dd, J=7.8 Hz and 3.1 Hz), 6.97 (2H, t, J=8.7 Hz), 7.09 (1H, s), 7.14 (2H, s), 4.91 (1H, dd, J=7.8 Hz and 3.1 Hz), 7.67 (1H, s); m/z EI+ 552(M+H).

Reference： [1]Patent: US5968934,1999,A

26
bis-(dibenzylideneacetone)palladium (O) [ No CAS ]
[ 6163-58-2 ]
[ 133720-60-2 ]
[ 57260-71-6 ]
[ 187795-32-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate; In toluene; Petroleum ether;	Tri-o-tolylphosphine (1.42 g) was added to a stirred suspension of bis (dibenzylideneacetone) palladium (O) (1.4 g) in toluene (480 ml) at ambient temperature under nitrogen. Sodium tert-butoxide (16.1 g) was added, followed by N-tert-butoxycarbonylpiperazine (26.6 g) and stirring was continued at ambient temperature for 5 minutes. <strong>[133720-60-2]7-Bromobenzo[b]furan</strong> (23.3 g) was added and the stirred mixture was heated under reflux for 20 hours and then cooled to ambient temperature. The organic solution was decanted from the palladium residues, then washed with brine (500 ml) and dried (MgSO4). The solvent was removed in vacuo and the residue was purified by flash column chromatography over silica using a 1:9 mixture of ether and petroleum ether (b.p. 60-80 C.) as eluant to give tert-butyl 4-(7-benzo[b]furanyl)piperazine-1-carboxylate (7.12 g) as a pale yellow solid, m.p. 98-100 C.

Reference： [1]Patent: US6114334,2000,A

27
[ 292638-84-7 ]
[ 98519-65-4 ]
[ 6163-58-2 ]
4-(2-Phenylethenyl)-7-chloroquinoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With triethylamine;palladium diacetate; In hexane; ethyl acetate;	EXAMPLE 2 4-(2-Phenylethenyl)-7-chloroquinoline STR8 A mixture of <strong>[98519-65-4]4-bromo-7-chloroquinoline</strong> (24.3 g, 0.1 mol), styrene (12.0 g, 0.125 mol), tri(o-tolyl) phosphine (0.4 g, 1.3 mmol), palladium acetate (0.2 g, 0.89 mol) and triethylamine (120 mls) was charged into a 300 ml stirred pressure vessel and heated at 120 C. for 17 hours. The mixture was cooled, filtered to remove triethylamine hydrobromide, and the solids washed with ethyl acetate (250 ml). Solvents were evaporated under reduced pressure and the residue dissolved in ethyl acetate (500 ml). The solution was washed with water and brine, and dried over anhydrous sodium sulphate. Evaporation of the solvent under reduced pressure and recrystallisation of the residue from ethyl acetate: hexane gave the product (13.5 g, 51%) as an orange solid, mp 120-122 C. Found: C, 76.50; H, 4.62; N, 5.38%; calculated: C, 76.84; H, 4.55; N, 5.27%

Reference： [1]Patent: US6117884,2000,A

28
[ 2680-03-7 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 143322-57-0 ]
(R)-5-trans-(2-N,N-Dimethylaminocarbonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	With triethylamine; In acetonitrile;	A. (R)-5-trans-(2-N,N-Dimethylaminocarbonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of N,N-dimethylacrylamide (134 muL, 1.3 mmol), tri-o-tolylphosphine (91 mg, 0.3 mmol), palladium (II) acetate (15 mg, 0.07 mmol), triethylamine (280 muL, 2 mmol) and <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> was dissolved in anhydrous acetonitrile (5 mL) and refluxed for 24 hours under nitrogen. The reaction was partitioned between ethyl acetate and aqueous sodium carbonate. The dried (Na2 SO4) organic phase was evaporated and the residue purified by column chromatography on silica gel, eluding with CH2 Cl2: MeOH: NH4 OH 96:3.5:0.5 to afford the title compound as a white foam (145 mg, 47%). Anal. Calcd for C19 H25 N3 O·1/9 CH2 Cl2: C, 71.56; H, 7.87; N, 13.10 %. Found: C,71.29; H,8.15; N,13.05.
47%	With triethylamine; In acetonitrile;	A. (R)-5-trans-(2-N,N-Dimethylaminocarbonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of N,N-dimethylacrylamide (134 muL, 1.3 mmol), tri-o-tolylphosphine (91 mg, 0.3 mmol), palladium (II) acetate (15 mg, 0.07 mmol), triethylamine (280 muL, 2 mmol) and <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> was dissolved in anhydrous acetonitrile (5 mL) and refluxed for 24 hours under nitrogen. The reaction was partitioned between ethyl acetate and aqueous sodium carbonate. The dried (Na2 SO4) organic phase was evaporated and the residue purified by column chromatography on silica gel, eluding with CH2 Cl2:MeOH:NH4 OH 96:3.5:0.5 to afford the title compound as a white foam (145 mg, 47%). Anal. Calcd for C19 H25 N3 O· 1/9CH2 Cl2: C,71.56; H,7.87; N,13.10%. Found: C,71.29; H,8.15; N,13.05.
47%	With triethylamine; In acetonitrile;	A. (R)-5-trans-(2-N,N-Dimethylaminocarbonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of N,N-dimethylacrylamide (134 muL, 1.3 mmol), tri-o-tolylphosphine (91 mg, 0.3 mmol), palladium (II) acetate (15 mg, 0.07 mmol), triethylamine (280 muL, 2 mmol) and <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> was dissolved in anhydrous acetonitrile (5 mL) and refluxed for 24 hours under nitrogen. The reaction was partitioned between ethyl acetate and aqueous sodium carbonate. The dried (Na2 SO4) organic phase was evaporated and the residue purified by column chromatography on silica gel, eluding with CH2 Cl2: MeOH: NH4 OH 96:3.5:0.5 to afford the title compound as a white foam (145 mg, 47%). Anal. Calcd for C19 H25 N3 O*1/9 CH2 Cl2: C,71.56; H,7.87; N,13.10%. Found: C,71.29; H,8.15; N,13.05.

47%	With triethylamine; In acetonitrile;	A. (R)-5-trans-(2-N,N-Dimethylaminocarbonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of N,N-dimethylacrylamide (134 muL, 1.3mmol), tri-o-tolylphosphine (91 mg, 0.3 mmol), palladium (II) acetate (15 mg, 0.07 mmol), triethylamine (280 muL, 2 mmol) and <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> was dissolved in anhydrous acetonitrile (5 mL) and refluxed for 24 hours under nitrogen. The reaction was partitioned between ethyl acetate and aqueous sodium carbonate. The dried (Na2 SO4) organic phase was evaporated and the residue purified by column chromatography on silica gel, eluding with CH2 Cl2: MeOH: NH4 OH 96:3.5:0.5 to afford the title compound as a white foam (145 mg, 47%). Anal. Calcd for C19 H25 N3 O·1/9 CH2 Cl2: C,71.56; H,7.87; N,13.10%. Found: C,71.29; H,8.15; N,13.05.
47%	With triethylamine; In acetonitrile;	A. (R)-5-trans-(2-N,N-Dimethylaminocarbonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of N,N-dimethylacrylamide (134 muL, 1.3 mmol), tri-o-tolylphosphine (91 mg, 0.3 mmol), palladium (II) acetate (15 mg, 0.07 mmol), triethylamine (280 muL, 2 mmol) and <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> was dissolved in anhydrous acetonitrile (5 mL) and refluxed for 24 hours under nitrogen. The reaction was partitioned between ethyl acetate and aqueous sodium carbonate. The dried (Na2 SO4) organic phase was evaporated and the residue purified by column chromatography on silica gel, eluding with CH2 Cl2: MeOH: NH4 OH 96:3.5:0.5 to afford the title compound as a white foam (145 mg, 47%). Anal. Calcd for C19 H25 N3 O. 1/9 CH2 Cl2: C, 71.56; H, 7.87; N, 13.10%. Found: C, 71.29; H, 8.15; N, 13.05.

Reference： [1]Patent: US5545644,1996,A
[2]Patent: US5578612,1996,A
[3]Patent: US5559246,1996,A
[4]Patent: US5559129,1996,A
[5]Patent: US5607951,1997,A

29
aqueous ammonia dichloromethane [ No CAS ]
[ 5535-52-4 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 143322-57-0 ]
(R)-5-(2-(4-methylphenylsulphonyl)-ethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In methanol; dichloromethane; acetonitrile;	EXAMPLE 34 (R)-5-[2-(4-Methylphenylsulphonyl)ethenyl]-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.40 g), 4-methylphenylvinylsulphone (0.273 g), tri-o-tolylphosphine (0.085 g), palladium (II) acetate (0.031 g), triethylamine (0.42 g), and acetonitrile (20 mL) was heated under reflux for 16 hours in an atmosphere of nitrogen. The mixture was cooled and partitioned between ethyl acetate and 10% aqueous sodium bicarbonate solution. The organic layer was washed with brine, dried (Na2 SO4) and evaporated. The residual orange oil was chromatographed on silica gel. Elution was commenced with dichloromethane/methanol (90:10), followed by aqueous ammonia dichloromethane/methanol/concentrated (90:10:0.25), gradually increasing the concentration of concentrated aqueous ammonia to 1%. The later product-containing fractions were evaporated to give the title compound as a foam (226 mg): [alpha]25D =+71 (methanol, c=0.10). Anal. Calcd for C23 H26 N2 O2 S. 0.15 CH2 Cl2: C,68.27; H,6.51; N,6.88. Found: C,68.26; H,6.54; N,6.99.

Reference： [1]Patent: US5578612,1996,A

30
[ 1889-59-4 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 143322-57-0 ]
[ 143321-72-6 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In acetonitrile;	EXAMPLE 28 (R)-5-(2-Ethylsulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.25 g), ethyl vinyl sulphone (0.14 g), tri-o-tolylphosphine (0.075 g), palladium (II) acetate (0.013 g), triethylamine (0.25 mL) and acetonitrile (3 mL) was heated under reflux for 17 hours in an atmosphere of nitrogen. The mixture was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/ethanol/concentrated aqueous ammonia (90:8:1) gave the title compound as a foam (0. 185 g): TLC (dichloromethane/-ethanol/concentrated aqueous ammonia, 90:10:1): Rf =0.5. Anal. Calcd for C18 H24 N2 O2 S. 0.2 CH2 Cl2: C,62.55; H,7.04; N,8.02. Found: C,62.65; H,6.94; N,7.92.
	With triethylamine; In acetonitrile;	EXAMPLE 28 (R)-5-(2-Ethylsulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.25 g), ethyl vinyl sulphone (0.14 g), tri-o-tolylphosphine (0,075 g), palladium (II) acetate (0.013 g), triethylamine (0.25 mL) and acetonitrile (3 mL) was heated under reflux for 17 hours in an atmosphere of nitrogen. The mixture was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/ethanol/concentrated aqueous ammonia (90:8:1) gave the title compound as a foam (0.185 g): TLC (dichloromethane/-ethanol/concentrated aqueous ammonia, 90:10:1): Rf =0.5. Anal. Calcd for C18 H24 N2 O2 S. 0.2 CH2 Cl2: C,62.55; H,7.04; N,8.02. Found: C,62.65; H,6.94; N,7.92.
	With triethylamine; In acetonitrile;	EXAMPLE 28 (R)-5-(2-Ethylsulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.25 g), ethyl vinyl sulphone (0.14 g), tri-o-tolylphosphine (0.075 g), palladium (II) acetate (0.013 g), triethylamine (0.25 mL) and acetonitrile (3 mL) was heated under reflux for 17 hours in an atmosphere of nitrogen. The mixture was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/ethanol/concentrated aqueous ammonia (90:8:1) gave the title compound as a foam (0.185 g): TLC (dichloromethane/-ethanol/concentrated aqueous ammonia, 90:10:1): Rf =0.5. Anal. Calcd for C18 H24 N2 O2 S. 0.2 CH2 Cl2: C,62.55; H,7.04; N,8.02. Found: C,62.65; H,6.94; N,7.92.

Reference： [1]Patent: US5545644,1996,A
[2]Patent: US5559129,1996,A
[3]Patent: US5559246,1996,A

31
[ 5535-48-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 143322-57-0 ]
3-[(2R)-1-methylpyrrolidin-2-yl] methyl}-5-[(E)-2-(phenylsulfonyl)ethenyl]-1H-indole hydrobromide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In acetonitrile;	EXAMPLE 31 (R)-5-(2-Benzenesulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole hydrobromide A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.25 g), phenylvinylsulphone (0.19 g), tri-o-tolylphosphine (0.075 g), palladium (II) acetate (0.0125 g), triethylamine (0.25 mL) and acetonitrile (2.5 mL) was heated under reflux for 42 hours in an atmosphere of nitrogen. The solvent was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/methanol/concentrated aqueous ammonia (90:10:1) gave the title compound as a foam (0.24 g): Anal. Calcd for C22 H24 N2 O2 S. HBr. 1/3 CH2 Cl2: C,54,77; H,5,29; N,5.72. Found: C,55.00; H,4.85; N,5.58.
	With triethylamine; In acetonitrile;	EXAMPLE 31 (R)-5-(2-Benzenesulphonylethenyl)-3-(N-methylpyrrolidin-2 -ylmethyl)-1H-indole hydrobromide A mixture of (R)-5-bromo-3-(N-methylpyrrolidin-2ylmethyl)-1H-indole (0.25 g), phenylvinylsulphone (0.19 g), tri-o-tolylphosphine (0. 075 g), palladium (II) acetate (0.0125 g), triethylamine (0.25 mL) and acetonitrile (2.5 mL) was heated under reflux for 42 hours in an atmosphere of nitrogen. The solvent was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/methanol/concentrated aqueous ammonia (90:10:1) gave the title compound as a foam (0.24 g): Anal. Calcd for C22 H24 N2 O2 S. HBr. 1/3 CH2 Cl2: C,54.77; H,5.29; N,5.72. Found: C,55.00; H,4.85;N,5.58.
	With triethylamine; In acetonitrile;	EXAMPLE 31 (R)-5-(2-Benzenesulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole hydrobromide A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.25 g), phenylvinylsulphone (0.19 g), tri-o-tolylphosphine (0.075 g), palladium (II) acetate (0.0125 g), triethylamine (0.25 mL) and acetonitrile (2.5 mL) was heated under reflux for 42 hours in an atmosphere of nitrogen. The solvent was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/methanol/concentrated aqueous ammonia (90:10:1) gave the title compound as a foam (0.24 g): Anal. Calcd for C22 H24 N2 O2 S. HBr. 1/3CH2 Cl2: C,54.77; H,5.29; N,5.72. Found: C,55.00; H,4.85; N,5.58.

With triethylamine; In acetonitrile;

EXAMPLE 31 (R)-5-(2-Benzenesulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole hydrobromide A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.25 g), phenylvinylsulphone (0.19 g), tri-o-tolylphosphine (0.075 g), palladium (II) acetate (0.0125 g), triethylamine (0.25 mL) and acetonitrile (2.5 mL) was heated under reflux for 42 hours in an atmosphere of nitrogen. The solvent was evaporated and the residue was chromatographed on silica gel. Elution with dichloromethane/methanol/concentrated aqueous ammonia (90:10:1) gave the title compound as a foam (0.24 g): Anal. Calcd for C22 H24 N2 O2 S. HBr. 1/3 CH2 Cl2: C,54.77; H,5.29; N,5.72. Found: C,55.00; H,4.85; N,5.58.

Reference： [1]Patent: US5545644,1996,A
[2]Patent: US5559129,1996,A
[3]Patent: US5578612,1996,A
[4]Patent: US5559246,1996,A

32
[ 5535-52-4 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 143322-57-0 ]
(R)-5-(2-(4-methylphenylsulphonyl)-ethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In methanol; dichloromethane; acetonitrile;	EXAMPLE 34 (R)-5-[2-(4-Methylphenylsulphonyl)ethenyl]-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.40 g), 4-methylphenylvinylsulphone (0.273 g), tri-o-tolylphosphine (0.085 g), palladium (II) acetate (0.031 g), triethylamine (0.42 g), and acetonitrile (20 mL) was heated under reflux for 16 hours in an atmosphere of nitrogen. The mixture was cooled and partitioned between ethyl acetate and 10% aqueous sodium bicarbonate solution. The organic layer was washed with brine, dried (Na2 SO4) and evaporated. The residual orange oil was chromatographed on silica gel. Elution was commenced with dichloromethane/methanol (90:10), followed by dichloromethane/methanol/concentrated aqueous ammonia (90:10:0.25), gradually increasing the concentration of concentrated aqueous ammonia to 1%. The later product-containing fractions were evaporated to give the title compound as a foam (226 mg): [alpha]25D =+71 (methanol, c=0.10). Anal. Calcd for C23 H26 N2 O2 S. 0.15 CH2 Cl2: C,68.27; H,6.51; N,6.88. Found: C,68.26; H,6.54; N,6.99.
	With triethylamine; In methanol; dichloromethane; acetonitrile;	EXAMPLE 34 (R)-5-[2-(4-Methylphenylsulphonyl)ethenyl]-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.40 g), 4-methylphenylvinylsulphone (0.273 g), tri-o-tolylphosphine (0.085 g), palladium (II) acetate (0.031 g), triethylamine (0.42 g), and acetonitrile (20 mL) was heated under reflux for 16 hours in an atmosphere of nitrogen. The mixture was cooled and partitioned between ethyl acetate and 10% aqueous sodium bicarbonate solution. The organic layer was washed with brine, dried (Na2 SO4) and evaporated. The residual orange oil was chromatographed on silica gel. Elution was commenced with dichloromethane/methanol (90:10), followed by dichloromethane/methanol/concentrated aqueous ammonia (90:10:0.25), gradually increasing the concentration of concentrated aqueous ammonia to 1%. The later product-containing fractions were evaporated to give the title compound as a foam (226 mg): [a]26D =+71 (methanol, c=0.10). Anal. Calcd for C23 H26 N2 O2 S. 0.15 CH2 Cl2: C,68.27; H,6.51; N,6.88. Found: C,68.26; H,6.54; N,6.99.
	With triethylamine; In methanol; dichloromethane; acetonitrile;	EXAMPLE 34 (R)-5-[2-(4-Methylphenylsulphonyl)ethenyl]-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.40 g), 4-methylphenylvinylsulphone (0.273 g), tri-o-tolylphosphine (0.085 g), palladium (II) acetate (0.031 g), triethylamine (0.42 g), and acetonitrile (20 mL) was heated under reflux for 16 hours in an atmosphere of nitrogen. The mixture was cooled and partitioned between ethyl acetate and 10% aqueous sodium bicarbonate solution. The organic layer was washed with brine, dried (Na2 SO4) and evaporated. The residual orange oil was chromatographed on silica gel. Elution was commenced with dichloromethane/methanol (90:10), followed by dichloromethane/methanol/concentrated aqueous ammonia (90:10:0.25), gradually increasing the concentration of concentrated aqueous ammonia to 1%. The later product-containing fractions were evaporated to give the title compound as a foam (226 mg): [alpha]25D =+71 (methanol, c =0.10). Anal. Calcd for C23 H26 N2 O2 S. 0.15 CH2 Cl2: C, 68.27; H,6.51; N,6.88. Found: C,68.26; H,6.54; N,6.99.

With triethylamine; In methanol; dichloromethane; acetonitrile;

EXAMPLE 34 (R)-5-[2-(4-Methylphenylsulphonyl)ethenyl]-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole A mixture of <strong>[143322-57-0](R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1H-indole</strong> (0.40 g), 4-methylphenylvinylsulphone (0.273 g), tri-o-tolylphosphine (0.085 g), palladium (II) acetate (0.031 g), triethylamine (0.42 g), and acetonitrile (20 mL) was heated under reflux for 16 hours in an atmosphere of nitrogen. The mixture was cooled and partitioned between ethyl acetate and 10% aqueous sodium bicarbonate solution. The organic layer was washed with brine, dried (Na2 SO4) and evaporated. The residual orange oil was chromatographed on silica gel. Elution was commenced with dichloromethane/methanol (90:10), followed by dichloromethane/methanol/concentrated aqueous ammonia (90:10:0.25), gradually increasing the concentration of concentrated aqueous ammonia to 1%. The later product-containing fractions were evaporated to give the title compound as a foam (226 mg): [alpha]25D =+71 (methanol, c =0.10). Anal. Calcd for C23 H26 N2 O2 S. 0.15 CH2 Cl2: C, 68.27; H, 6.51; N, 6.88. Found: C, 68.26; H, 6.54; N, 6.99.

Reference： [1]Patent: US5545644,1996,A
[2]Patent: US5559246,1996,A
[3]Patent: US5559129,1996,A
[4]Patent: US5607951,1997,A

33
[ 24167-51-9 ]
[ 3375-31-3 ]
[ 813-19-4 ]
[ 6163-58-2 ]
[ 153435-27-9 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In dichloromethane; ethyl acetate; acetonitrile;	PREPARATION 1 3-N,N-Dimethylcarbamoylphenyltri-n-butylstannane STR87 A mixture of <strong>[24167-51-9]3-bromo-N,N-dimethylbenzamide</strong> (2.74 g, 12.01 mmol), tri-o-tolylphosphine (960 mg, 3.15 mmol), palladium (II) acetate (120 mg, 0.54 mmol), triethylamine (3.20 ml, 22.96 mmol) and hexa-n-butyldistannane (6.96 g, 4.6 ml, 12.00 mmol) in anhydrous acetonitrile (40 ml) was heated under reflux, under nitrogen, for 18 hours. The reaction mixture was then evaporated under reduced pressure and dichloromethane (25 ml) was added. The resultant solution was washed with aqueous sodium carbonate, dried (Na2 SO4) and evaporated. The residue was purified by column chromatography on silica gel eluding initially with hexane until the tri-o-tolylphosphine and unreacted hexabutyldistannane had been eluted and then with hexane/ethyl acetate (1:1) to afford, after combination and evaporation of the appropriate fractions, the title compound as a light brown oil, (1.90 g). Found: C, 57.39; H, 8.41; N, 3.04; C21 H37 NOSn requires: C, 57.56; H, 8.51; N, 3.20%. 1 H-NMR (CDCl3): delta=0.90 (t,9H), 1.05 (t,6H), 1.30 (m,6H), 1.52 (m,6H), 2.95 (s,3H), 3.12 (s,3H), 7.30-7.38 (m,2H), 7.40-7.55 (m,2H) ppm.

Reference： [1]Patent: US5502065,1996,A

34
[ 115-18-4 ]
[ 6163-58-2 ]
[ 143322-57-0 ]
[ 167302-44-5 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In acetonitrile;	EXAMPLE 1 5-(3-Hydroxy-3-methyl-1-but-1-enyl)-3-(N-methyl-2(R)-pyrrolidinylmethyl)-1H-indole A stirred solution of 5-bromo-3-(N-methyl-2(R)-pyrrolidinylmethyl)-1H-indole (WO-A-92/06973; 879 mg, 3.0 mmol), 2-methylbut-3-en-2-ol (0.408 ml, 3.9 mmol), tri-o-tolylphosphine (273 mg, 0.90 mmol), palladium(II) acetate (45 mg, 0.20 mmol), triethylamine (0.84 ml, 6.0 mmol) and acetonitrile (50 ml), under nitrogen, was heated under reflux for 24 hours, allowed to cool, then partitioned between ethyl acetate and 2M aqueous sodium carbonate solution. The organic phase was separated, washed sequentially with 2M aqueous sodium carbonate solution (2) and brine (1), dried (Na2 SO4) and evaporated under reduced pressure. The crude product was purified by column chromatography on silica gel, eluding with a solvent gradient of 0.880 aqueous ammonia:methanol: dichloromethane (0:5:95 to 0.5:5:95), to afford the title compound as a solid (226 mg), m.p. 155-158 C. Rf 0.10 (SS 1). [alpha]D25 +81 (c=0.1, CH3 OH). Found: C,75.27; H,8.96; N,8.99. C19 H26 N2 O; 0.25 H2 O requires C,75.33; H,8.82; N,9.25%.

Reference： [1]Patent: US5607960,1997,A

35
[ 18869-30-2 ]
[ 6163-58-2 ]
[ 140-88-5 ]
ethyl 4-bromostilbene-4'-acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tributyl-amine;palladium diacetate; In para-xylene;	EXAMPLE 3 Ethyl 4-bromostilbene-4'-acrylate. 25.8 g (0.1 mol) of 4,4'-dibromostilbene, 10 g (0.1 mol) of ethyl acrylate, 18.5 g (0.1 mol) of tri-n-butylamine, 0.224 g (0.001 mol) of palladium acetate and 0.6 g (0.002 mol) of tri-o-tolylphosphine are added under argon to 50 ml of p-xylene. The reaction mixture is stirred at 90 C. for 4 hours. Working up gives 2 g (6% of theory) of ethyl 4-bromostilbene-4'-acrylate. Melting point 166.9 C.

Reference： [1]Patent: US4918215,1990,A

36
[ 16817-43-9 ]
[ 530-93-8 ]
[ 6163-58-2 ]
(+/-)-(1RS)-1-(4-Chloro-3-methoxyphenyl)-3,4-dihydro-2(1H)-naphthalenone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium hydrogencarbonate;palladium diacetate; In N-methyl-acetamide; ethyl acetate;	EXAMPLE II Preparation of (+-)-(1RS)-1-(4-Chloro-3-methoxyphenyl)-3,4-dihydro-2(1H)-naphthalenone (7) STR14 Charge an oven dried, argon flushed 25-mL two-necked round bottomed flask equipped with a stirring bar with beta-tetralone (1.3095 grams, 8.9575 mmoles) and 5 mL dry dimethylformamide. Cool to 0 C. with an ice bath, add sodium hydride (0.4299 grams, 8.9575 mmoles, 50% oil dispersion) and stir for 25 minutes. Filter the solution through a 5 mL syringe equipped with a bed of celite (dried in an oven) via a double-ended needle into an oven dried, argon flushed 25-mL round bottomed flask equipped with a stirring bar and reflux condenser which had been charged with 4-bromo-2-methoxy-1-chlorobenzene (1.5871 grams, 7.166 mmoles), palladium acetate (0.0079 grams 0.0350 mmoles) and tri(omicron-tolyl)phosphine (0.0213 grams, 0.070 mmoles). Heat at about 125 C. (oil bath) for 21 hours, cool to RT and add ethyl acetate and 2N HCl. Separate the layers, extract the aqueous layers with two portions of ethyl acetate, wash the combined organic layers with saturated sodium bicarbonate solution followed by saturated salt solution, dry over magnesium sulfate and concentrate using a Buchi rotavapor to produce the named product.

Reference： [1]Patent: US4992591,1991,A

37
[ 10075-50-0 ]
[ 7700-07-4 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
2-(1H-Indol-5-yl)-N,N-dimethylethenesulphonamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In acetonitrile;	(i) 2-(1H-Indol-5-yl)-<strong>[7700-07-4]N,N-dimethylethenesulphonamide</strong> A mixture of 5-bromoindole (7.7 g), <strong>[7700-07-4]N,N-dimethylethenesulphonamide</strong> (5.3 g) triethylamine (15 ml), acetonitrile (5 ml), palladium (II) acetate (0.35 g) and tri-o-tolylphosphine (0.95 g) was heated at 100 C. in an autoclave for 3 h. The resulting cooled mixture was partitioned between hydrochloric acid (2N, 300 ml) and ethyl acetate (2*150 ml). The combined extracts were dried (Na2 SO4) and evaporated in vacuo. The residue was purified by `flash` chromatography (V, 7 cm col.) to give the title compound as a crystalline solid (3.8 g) m.p. 148-150 C.

Reference： [1]Patent: US4994483,1991,A

38
[ 79-10-7 ]
[ 6163-58-2 ]
[ 131818-17-2 ]
[ 197073-43-1 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium(II) chloride; In dichloromethane; water;	To a mixture of 27 g of 4-(t-butoxycarbonylamino)-bromobenzene, 0.18 g of palladium chloride, 1.25 g of tri-O-tolylphosphine and 50 ml of triethylamine is added 9.5 ml of acrylic acid followed by 25 ml of triethylamine. The reaction mixture is heated under reflux for 3 hours. Methylene chloride (250 ml) is added, the reaction mixture is filtered and evaporated to dryness. The residue is suspended in water, the suspension is washed with toluene, concentrated HCl is added while cooling to pH5. The resulting 4-(t-butoxycarbonylamino)-cinnamic acid is collected, washed with water and dried; m.p. 175-177.

Reference： [1]Patent: US5096919,1992,A

39
[ 292638-84-7 ]
[ 1073-39-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 138540-82-6 ]

Yield	Reaction Conditions	Operation in experiment
	With tributyl-amine; In acetonitrile;	EXAMPLE 1 Preparation of 1-Phenyl-2-(4-Benzocyclobutyl)ethene STR17 A solution of 2.4 g 4-bromobenzocyclobutane, 1.4 g styrene, 2.4 g tri-n-butylamine, 29 mg palladium (II) acetate, 100 mg of tri-o-tolylphosphine and 10 ml acetonitrile is stirred under nitrogen atmosphere at reflux for three hours. The reaction mixture is poured into 60 ml 10 percent HCl. The product is isolated by filtration, dried, recrystallized in ethanol, and isolated. About 2.10 g of greenish monomer product is prepared.

Reference： [1]Patent: US4724260,1988,A

40
4-vinylbenzocyclobutene [ No CAS ]
[ 74-85-1 ]
[ 1073-39-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 99717-87-0 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; triethylamine;hexane; In diethyl ether; water; acetonitrile;	EXAMPLE 4 Preparation of 4-Vinylbenzocyclobutane STR20 Into a 450 ml Parr pressure reactor, 100 ml of acetonitrile, and 0.6 g of freshly distilled triethylamine are added. The mixture is purged with nitrogen gas through a sparge tube for 15 minutes to remove air. To the reactor, 0.98 g of 4-bromobenzocyclobutane, 0.04 g of palladium (II) acetate, 0.17 g of tri-o-tolylphosphine are added and the reactor is sealed. The reactor is then pressurized with 250 psig ethylene, and is then vented. The reactor is pressurized with 2 more charges of 250 psig ethylene and is vented after each charge. The vessel is then pressurized to 250 psig ethylene, and held there. The mixture is then heated to 125 C. and is mechanically stirred for 16 hours. The reaction mixture is allowed to cool and the remaining ethylene is vented. The reaction mixture is worked up by washing in 100 ml diethyl ether, and this mixture is washed twice with 100 ml of water, once with 100 ml of 5 percent hydrochloric acid, once more with 100 ml of water, and is then dried over magnesium sulfate. The solvent is removed. The product is analyzed by gas chromatography, and it is determined that approximately 70 percent of the 4-bromopbenzocyclobutane is converted to 4-vinylbenzocyclobutene. The reaction mixture is passed through a 100 ml column of silica gel in the presence of hexane as an eluent. The hexane is removed on a rotary evaporator and the product is recovered.

Reference： [1]Patent: US4724260,1988,A

41
[ 622-97-9 ]
[ 1073-39-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 138519-05-8 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; tributyl-amine; In acetonitrile;	EXAMPLE 7 Preparation of 1-(4-methylphenyl)-2-(4-benzocyclobutyl)ethene STR23 A solution of 3.0 g 4-bromobenzocyclobutane, 1.9 g 4-methylstyrene, 3.0 g tri-n-butylamine, 150 mg tri-o-tolylphosphine, 36 mg palladium (II) acetate, and 10 ml of acetonitrile is stirred at reflux under nitrogen for 4 hours. The reaction mixture is poured into 60 ml of 10 percent HCl. The product is isolated by filtration, dried, recrystallized from ethanol, and isolated. About 2.9 g of monomer is prepared.

Reference： [1]Patent: US4724260,1988,A

42
[ 827-54-3 ]
[ 1073-39-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
1-(2-Naphthyl)-2-(4-Benzocyclobutyl)ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; tributyl-amine; In acetonitrile;	EXAMPLE 2 Preparation of 1-(2-Naphthyl)-2-(4-Benzocyclobutyl)ethene STR18 A solution of 3.0 g 4-bromobenzocyclobutane, 2.5 g 2-vinylnaphthalene, 3.0 g tri-n-butylamine, 150 mg tri-o-tolylphosphine, 36 mg palladium (II) acetate, and 10 ml acetonitrile is stirred at reflux under nitrogen atmosphere for 4 hours. The reaction mixture is poured into 60 ml of 10 percent HCl. The product is isolated by filtration, dried, recrystallized from ethanol, and isolated. About 1.8 g of monomer is prepared.

Reference： [1]Patent: US4724260,1988,A

43
[ 1746-23-2 ]
[ 1073-39-8 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
1-p-tert-butylphenyl-2-(4-benzocyclobutyl)ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; tributyl-amine; In acetonitrile;	EXAMPLE 3 Preparation of 1-(p-tert-butylphenyl)-2-(4-benzocyclobutyl)ethene STR19 A solution of 3.0 g 4-bromobenzocyclobutane, 2.6 g 4-tert-butylstyrene, 3.0 g tri-n-butylamine, 150 mg tri-o-tolylphosphine, 36 mg palladium (II) acetate, and 10 ml acetonitrile is stirred under nitrogen at reflux for 4 hours. The reaction mixture is poured into 60 ml of 10 percent HCl. The product is isolated by filtration, dried, recrystallized from ethanol, and isolated. About 1.8 g of monomer is prepared.

Reference： [1]Patent: US4724260,1988,A

44
[ 100-69-6 ]
[ 381248-06-2 ]
[ 6163-58-2 ]
3-(2-Pyridylethenyl)-5-(pyridin-2-yl)-1-phenyl-1,2-dihydropyridin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In acetonitrile;	Example 187. 3-(2-Pyridylethenyl)-5-(2-pyridyl)-1-phenyl-1,2-dihydropyridin-2-one 23mg of <strong>[381248-06-2]3-bromo-5-(2-pyridyl)-1-phenyl-1,2-dihydropyridin-2-one</strong> was dissolved in 20ml of acetonitrile.To the mixture were added 0.2mg of palladium acetate, 4.3mg of tri-o-tolylphosphine and 0.04ml of triethylamine, followed by stirring at 110C in nitrogen atmosphere overnight. To the mixture was added 9.2mg of 2-vinylpyridine, followed by stirring at 110C in nitrogen atmosphere for 5 hours. After cooling to room temperature, the reaction mixture was poured into water, followed by extracting with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was purified by silica gel chromatography (hexane/ethyl acetate system), to give 2mg of the title compound. 1H-NMR (400MHz, CDCl3); delta(ppm) 7.12-7.16(m,1H), 7.18-7.23(m,1H), 7.36(d,1H), 7.44-7.51(m,3H), 7.51-7.55(m,2H), 7.57-7.60(m,1H), 7.64(dt,1H), 7.70-7.79(m,1H), 7.78-7.82(m,1H), 8.03-8.07(m,1H), 8.24(d,1H), 8.28(d,1H), 8.57-8.63(m,2H). ESI-Mass; 352 [M++H]

Reference： [1]Patent: EP1300396,2003,A1

45
[ 1122-70-9 ]
[ 255847-81-5 ]
[ 6163-58-2 ]
1-[(4-cyano-5-methyl-4-phenyl)hexyl]-4-{2-[2-(6-methyl-2-pyridyl)vinylphenoxy]ethyl}piperazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With triethylamine;palladium diacetate; In water; N,N-dimethyl-formamide;	Example 118 Synthesis of 1-[(4-cyano-5-methyl-4-phenyl)hexyl]-4-{2-[2-(6-methyl-2-pyridyl)vinylphenoxy]ethyl}piperazine In a nitrogen atmosphere, 1-[(4-cyano-5-methyl-4-phenyl)hexyl)-4-[2-(2-bromophenoxy)ethyl] piperazine 100 mg, 6-vinyl-2-methylpyridine 49 mg, palladium acetate 4.6 mg and tris(2-methylphenyl) phosphine 12.5 mg were dissolved in N,N-dimethylformamide 4.0 ml, and triethylamine 1 ml was added thereto, and the mixture was stirred for 10 hours under reflex with heating. The reaction mixture was cooled, filtered through Celite, and partitioned by adding water and diethylether. The organic layer was washed with water and then with brine, dried over magnesium sulfate anhydride and evaporated. The residues were purified by NH silica gel column chromatography (hexane/ethyl acetate system), whereby the title compound (115 mg, 100 %) was obtained as a colorless oil.

Reference： [1]Patent: EP1099692,2001,A1

46
PdCl₂(p(o-tolyl)3)2 [ No CAS ]
bis(acetonitrile) Pd(II) chloride(53 mg, 0.206 mmol) [ No CAS ]
[ 117572-79-9 ]
[ 177-11-7 ]
[ 6163-58-2 ]
1-(5-cyano-2-methoxyphenyl)-4-piperidone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium hexamethyldisilazane; In tetrahydrofuran; 1,4-dioxane; hexane; ethyl acetate; toluene;	EXAMPLE 5A 1-(5-cyano-2-methoxyphenyl)-4-piperidone 1,4-Dioxa-8-azaspiro[4.5]decane (1.47 g, 10.28 mmol), sodium bis(trimethylsilyl)amide (1 N in THF, 12 ml), and PdCl2(p(o-tolyl)3)2 [2 mol % catalyst prepared from bis(acetonitrile) Pd(II) chloride(53 mg, 0.206 mmol) and tri(o-tolyl)phosphine (125 mg, 0.52 mmol)] were added to a solution of <strong>[117572-79-9]3-bromo-4-methoxybenzonitrile</strong> (1.82 g, 8.58 mmol) in toluene (40 ml). The reaction was stirred for 5 hours at 100 C. The reaction was concentrated in vacuo, diluted with water, and extracted with methylene chloride. The organic extract was concentrated in vacuo, and the residue purified by chromatography on silica gel using hexane/ethyl acetate (80/20) as the eluent to give 1-(5-cyano-2-methoxyphenyl)-4-piperidone ethylene ketal (900 mg, 38%). This ketal was dissolved in dioxane (15 ml) and HCl (6 N, 2.2 ml) and stirred at 100 C. for 2 h. The solution was cooled, quenched with saturated aqueous NaHCO3. The mixture was extracted with methylene chloride, concentrated in vacuo, and purified by chromatography on silica gel using hexane/ethyl acetate (80/20) as the eluent to give 1-(5-cyano-2-methoxyphenyl)-4-piperidone (125 mg, 19%).

Reference： [1]Patent: US6225324,2001,B1

47
[ 292638-84-7 ]
hexanes-EtOAc [ No CAS ]
[ 6163-58-2 ]
[ 215453-51-3 ]
1-Chloro-7-(2-phenyl-E-ethenyl)isoquinoline [ No CAS ]
1-chloro-(2-phenylethen-1-yl)isoquinoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In N,N-dimethyl-formamide;	Preparation 43 1-Chloro-7-(2-phenyl-E-ethenyl)isoquinoline A solution of <strong>[215453-51-3]7-bromo-1-chloroisoquinoline</strong> (200 mg, 0.80 mmol), styrene (94 mg, 0.90 mmol), tri-o-tolylphosphine (30 mg, 12 mol %), palladium (II) acetate (Pd(OAc)2) (10 mg, 5 mol %) and triethylamine (0.34 mL, 2.5 mmol) in DMF (0.75 mL) were placed in a MOS-2000 (650 W) microwave and irradiated at full power for 7*40s (reaction monitored by TLC). The mixture was poured into water and extracted with EtOAc. The combined organic layers were dried over MgSO4, evaporated in vacuo and the residue was purified by column chromatography upon silica gel using hexanes-EtOAc (100:0 to 95:5) as eluant to give 1-chloro-(2-phenylethen-1-yl)isoquinoline (135 mg, 0.508 mmol) as a yellow solid. M.Pt. 118-121 C.; 1H (delta, CDCl3, 300 MHz) 7.3-7.35 (3H, m), 7.44 (2H, dd), 7.55-7.65 (3H, m), 7.8 (1H, d), 8.0 (1H, d), 8.25 (1H, d), 8.3 (1H, s); LRMS 266, 268 (MH); El.Anal. Found: C, 76.87; H, 4.61; N, 5.18. Calcd for C17H12ClN: C, 76.84; H, 4.55; N, 5.27.

Reference： [1]Patent: US6248738,2001,B1

48
[ 20611-21-6 ]
[ 699-08-1 ]
[ 6163-58-2 ]
[ 7143-01-3 ]
[2-(phenylsulfonyl)ethenyl]-4-ethoxybenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With triethylamine;palladium diacetate; In acetonitrile;	Example 11 To 0.186 g (1.0 mmol) of 2-(phenylsulfonyl)ethanol, 3 ml of acetonitrile was added, followed by 0.19 g (1.1 mmol) of methanesulfonic anhydride and 0.56 ml (4.0 mmol) of triethylamine, and the mixture was stirred for 5 hours at the internal temperature of 50 C. Subsequently, 0.37 g (1.5 mmol) of p-iodophenetole, 0.011g (0.05 mmol) of palladium acetate, and 0.067 g (0.22 mmol) of tri(o-tolyl)phosphine were added thereto, and the mixture was then refluxed for 17 hours. After cooled to room temperature, the reaction mixture was concentrated and purified by column chromatography (hexane/ethyl acetate=80/20) to obtain 0.158 g of [2-(phenylsulfonyl)ethenyl]-4-ethoxybenzene. Yield: 55%.

Reference： [1]Patent: US6201131,2001,B1

49
palladium tetraammine di(hydrogen carbonate) [ No CAS ]
[ 6163-58-2 ]
[ 69861-71-8 ]

Yield	Reaction Conditions	Operation in experiment
98%	In methanol; for 3h;Heating / reflux;	Palladium tetrammine dihydrogencarbonate was reacted with 3 mole equivalents of tris(orffto- tolyl)phosphine (Po-tol3) in methanol at reflux under N2 for 3 hours. The reaction mixture was cooled to O0C and filtered to give product as bright yellow crystal. The filtrate was evaporated to 10ml, and filtered to give more yellow precipitate. Total yield = 98%. NMR and IR indicate pure product as Pd(Po-tol3)2 (Pd(O)).

Reference： [1]Patent: WO2007/29031,2007,A1 .Location in patent: Page/Page column 5

50
[ 98198-48-2 ]
[ 6163-58-2 ]
[ 140-88-5 ]
ethyl (E)-3-(6-amino-4-methylpyridin-3-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With N-ethyl-N,N-diisopropylamine;palladium diacetate; In ethyl acetate; propiononitrile;	b) Ethyl (E)-3-(6-amino-4-methylpyridin-3-yl)acrylate To a stirred solution of <strong>[98198-48-2]2-amino-5-bromo-4-methylpyridine</strong> (10 g, 54 mmole) in propionitrile (50 mL) was added ethyl acrylate (17 mL, 157 mmole), DIEA (19 mL, 106 mmole), palladium(II) acetate (0.61 g, 2.7 mmole) and tri-o-tolylphosphine (1.64 g, 5.4 mmole). The reaction was purged with argon and heated at reflux for 6 hr, then was cooled to RT and concentrated to dryness under vacuum. The resulting residue was taken up in ethyl acetate and filtered through a pad of silica gel. The filtrate was concentrated and the remaining residue was triturated with 1:1 Et2O/petroleum ether (50 mL), filtered, and dried under vacuum to give the title compound (6.50 g, 59%) as a pale yellow solid: 1H NMR (400 MHz, DMSO-d6) delta 8.31 (s, 1 H), 7.66 (d, J = 16.0 Hz, 1 H), 6.40 (br s, 2 H), 6.32 (d, J. = 16.0 Hz, 1 H), 6.28 (s, 1 H), 4.15 (q, 2 H), 2.24 (s, 3 H), 1.24 (t, 3 H).

Reference： [1]Patent: EP1226138,2004,B1

51
[ 289039-82-3 ]
BnEt₃NCl [ No CAS ]
[ 6163-58-2 ]
silver carbonate [ No CAS ]
[ 397329-44-1 ]

Yield	Reaction Conditions	Operation in experiment
17%	With sodium bicarbonate;palladium diacetate; In water; N,N-dimethyl-formamide;	(202-2) Under nitrogen atmosphere, a suspension of <strong>[289039-82-3]methyl 5-chloro-2-iodobenzoate</strong> (Example 109-9) (220 mg), the compound of Example 202-1 (200 mg), Pd(OAc)2 (22.9 mg), BnEt3NCl (171 mg), sodium hydrogen carbonate (130 mg), tri-o-tolylphosphine (68.4 mg) in DMF (4.0 mL) was stirred at 80C for 4 hours, and stirred at 100C for 11 hours, during which silver (I) carbonate (207 mg) was added thereto. The mixture was cooled to room temperature, and the mixture was filtered. Water was added to the filtrate, and the mixture was extracted with ethyl acetate/toluene. The organic layer was washed with water and a saturated brine, and dried over MgSO4. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column (hexane/ethyl acetate = 7/1 ? 5/1) to give methyl 5-chloro-2-{(1E)-4-[2-(4-methoxybenzoyl)-4-methyl-1H-pyrrol-1-yl]-1-butenyl}benzoate (55.0 mg, 17 %). 1H NMR (CDCl3, 400MHz) delta 7.81 (d, 1H, J=2.2Hz), 7.77 (d, 2H, J=8.8Hz), 7.36 (d, 1H, J=8.5Hz), 7.32 (dd, 1H, J=2.2, 8.5Hz), 7.10 (d, 1H, J=15.7Hz), 6.90 (d, 2H, J=8.8Hz), 6.77 (d, 1H, J=1.4Hz), 6.51 (d, 1H, J=1.4Hz), 6.08 (dt, 1H, J=15.7, 7.1Hz), 4.49 (t, 2H, J=7.1Hz), 3.89 (s, 3H), 3.87 (s, 3H), 2.72 (dt, 2H, J=7.1, 7.1Hz), 2.07 (s, 3H).

Reference： [1]Patent: EP1479384,2004,A1

52
[ 300-57-2 ]
[ 890315-72-7 ]
[ 6163-58-2 ]
tert-butyl 2-nitro-4-(3-phenyl-1-propenyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In toluene;	Referential Example 14 19 mg of palladium acetate (II) was added to 5 mL of toluene solution containing 0.50 g of <strong>[890315-72-7]tert-butyl 4-bromo-2-nitrobenzoate</strong>, 50 mg of tri(o-tolyl)phosphine, 0.44 mL of allylbenzene and 0.46 mL of triethylamine, and the resulting mixture was heated to reflux under nitrogen atmosphere for 2 hours. After the reaction mixture was cooled to room temperature, 20 mg of palladium acetate (II) was added and the resulting mixture was heated to reflux for 7 hours. After the reaction mixture was cooled to room temperature, insoluble were removed by filtration, and the solvent was evaporated under reduced pressure. The obtained residue was purified with silica gel column chromatography [eluent; hexane:ethyl acetate = 30:1] to obtain 0.31 g of tert-butyl 2-nitro-4-(3-phenyl-1-propenyl)benzoate.

Reference： [1]Patent: EP1820795,2007,A1

53
[ 894853-20-4 ]
[ 6163-58-2 ]
[ 129686-16-4 ]
(E)-N-((1,3-dimethyl-1H-indol-1-yl)methyl)-N-methyl-3-(7-oxo-5,6,7,8-tetrahydro-1,8-napthyridin-3-yl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With N-ethyl-N,N-diisopropylamine;palladium diacetate; In propiononitrile;	b) (E)-N-(1,3-Dimethyl-1H-indol-2-ylmethyl)-N-methyl-3-(7-oxo-5,6,7,8-tetrahydro[1,8]naphthyridin-3-yl)acrylamide To a stirred solution of N-(1,3-dimethyl-1H-indol-2-ylmethyl)-N-methylacrylamide (1.7 g, 7 mmole) in propionitrile (50 mL) was added <strong>[129686-16-4]6-bromo-3,4-dihydro-1H-1,8-naphthyridin-2-one</strong> (1.16 g, 5.1 mmole), DIEA (1.8 mL, 10.3 mmole), palladium(II) acetate (112 mg, 0.5 mmole), and tri-o-tolylphosphine (304 mg, 1.0 mmole). The reaction was purged with argon and heated at reflux for 16 hr, then was cooled to RT and concentrated under vacuum. Purification by flash chromatography on silica gel (5% methanol/CHCl3). trituration with ethyl acetate, filtration, and drying under vacuum gave the title compound (1.17 g, 59%) as an off-white solid: LCMS (ES) m/e 389.2 (M + H)+.

Reference： [1]Patent: EP1226138,2004,B1

54
[ 890315-72-7 ]
[ 768-56-9 ]
[ 6163-58-2 ]
tert-butyl 2-nitro-4-(4-phenyl-1-butenyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine;palladium diacetate; In toluene;	Referential Example 15 19 mg of palladium acetate (II) was added to 5 mL of toluene solution containing 0.50 g of <strong>[890315-72-7]tert-butyl 4-bromo-2-nitrobenzoate</strong>, 50 mg of tri(o-tolyl)phosphine, 0.50 mL of 4-phenyl-1-butene and 0.46 mL of triethylamine, and the resulting mixture was heated to reflux under nitrogen atmosphere for 4 hours and 30 minutes. After the reaction mixture was cooled to room temperature, 20 mg of palladium acetate (II) was added and the resulting mixture was heated to reflux for 5 hours and 30 minutes. After cooled to room temperature, the reaction mixture was purified with silica gel column chromatography [eluent; hexane:ethyl acetate = 30:1] to obtain 0.35 g of tert-butyl 2-nitro-4-(4-phenyl-1-butenyl)benzoate.

Reference： [1]Patent: EP1820795,2007,A1

55
[ 1450-85-7 ]
{Cu(tri-o-tolylphosphine)Br}4 [ No CAS ]
[ 6163-58-2 ]
[ 137708-58-8 ]

Reference： [1]Inorganica Chimica Acta,1991,vol. 186,p. 199 - 204

56
[ 1450-85-7 ]
{Cu(tri-o-tolylphosphine)I}n [ No CAS ]
[ 6163-58-2 ]
{(pyrimidine-2-thione)(tri-ortho-tolylphosphine)copper(I) iodide} [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1992,vol. 193,p. 129 - 136

57
[ 1450-85-7 ]
{Cu(tri-ortho-tolylphosphine)Cl}n [ No CAS ]
[ 6163-58-2 ]
{(pyrimidine-2-thione)(tri-ortho-tolylphosphine)copper(I) chloride} [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1992,vol. 193,p. 129 - 136

58
[ 6163-58-2 ]
[ 32005-36-0 ]
[ 69861-71-8 ]

Reference： [1]Journal of the American Chemical Society,1994,vol. 116,p. 5969 - 5970
[2]Journal of the American Chemical Society,2017,vol. 139,p. 11662 - 11665

59
tris(dibenzylideneacetone)dipalladium [ No CAS ]
Pd((C₆H₅CHCH)2C(O))3 [ No CAS ]
[ 6163-58-2 ]
[ 69861-71-8 ]

Reference： [1]Organometallics,1995,vol. 14,p. 3030 - 3039

60
[ 40691-33-6 ]
[ 6163-58-2 ]
[ 69861-71-8 ]

Reference： [1]European Journal of Inorganic Chemistry,1998,p. 29 - 35

61
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 172418-32-5 ]

Reference： [1]Angewandte Chemie - International Edition in English,1995,vol. 34,p. 1844 - 1848

62
[ 6163-58-2 ]
9-phenylcarbazol-3-boronic acid [ No CAS ]
[ 18869-30-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;palladium diacetate; In 1,2-dimethoxyethane;	1.0 g (3.0 mmol) of (E)-4,4'-dibromostilbene obtained by the synthesis scheme (f-2) in Embodiment 1, 1.9 g (6.6 mmol) of 9-phenylcarbazol-3-boronic acid, which was obtained as described above, 0.014 g (0.066 mmol) of palladium acetate (II), and 0.14 g (0.45 mmol) of tris(ortho-tolyl)phosphine were put into a 100 mL three-necked flask, and the air in the flask was replaced with nitrogen. Then, 20 mL of ethylene glycol dimethyl ether (DME) and 10 mL (20 mmol) of potassium carbonate solution (2.0 mol/L) were added to the mixture.

Reference： [1]Patent: US2008/145700,2008,A1

63
potassium phosphate monohydrate [ No CAS ]
[ 523-27-3 ]
[ 103986-53-4 ]
[ 6163-58-2 ]
[ 885516-13-2 ]

Yield	Reaction Conditions	Operation in experiment
	palladium diacetate; In 1,4-dioxane; water; toluene;	a) Synthesis of the Atropisomer Mixture of Anthracene Derivative A1 1.83 g (6 mmol) of tris-o-tolylphosphine and then 225 mg (1 mmol) of palladium(II) acetate were added to a degassed, well-stirred suspension of 74.4 g (400 mmol) of 4-methylnaphthalene-1-boronic acid, 33.6 g (100 mmol) of 9,10-dibromoanthracene and 104.3 g (420 mmol) of potassium phosphate monohydrate in a mixture of 300 ml of toluene, 150 ml of dioxane and 400 ml of water, and the mixture was subsequently refluxed for 16 h. After the reaction mixture had been cooled to room temperature, the precipitated solid was filtered off with suction and washed three times with 200 ml of water each time and three times with 100 ml of ethanol each time. After drying in vacuo (1 mbar; 80 C., 16 h), the product was extracted with chloroform through a glass-fibre extraction thimble (pore size 0.1 pm) in a Soxhlett extractor in order to remove traces of palladium. The chloroform was concentrated to a volume of 100 ml, and 500 ml of ethanol were added. The resultant precipitate was filtered off with suction and washed with ethanol. The yield of crude product A1 was 41.3 g (90 mmol), 90.0% of theory.

Reference： [1]Patent: US2009/72712,2009,A1

64
tris(dibenzylideneacetone)dipalladium ⁽⁰⁾ [ No CAS ]
[ 1123194-98-8 ]
[ 79-06-1 ]
[ 6163-58-2 ]
[ 1123194-94-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate; triethylamine; In N,N-dimethyl-formamide; toluene;	Synthesis of (E)-3-[6-methoxy-5-(4-methyl-1H-imidazol-1-yl)pyridin-2-yl]acrylamide Triethylamine (52 ml) was added to a suspension of <strong>[1123194-98-8]6-bromo-2-methoxy-3-(4-methyl-1H-imidazol-1-yl)pyridine</strong> (49.8 g), tris(dibenzylideneacetone)dipalladium (0) (5.11 g), tri-o-tolylphosphine (3.41 g) and acrylamide (14.5 g) in N,N-dimethyl formamide (260 ml). The reaction solution was stirred at 100C for 50 minutes. The reaction solution was returned to room temperature and then filtered through celite. The filter cake was sequentially washed with N,N-dimethylformamide, methanol, a 50% N,N-dimethylformamide solution and N,N-dimethylformamide. The resulting filtrate was filtered through celite again, and the filtrate was concentrated under reduced pressure. Toluene was added to the residue, and the reaction solution was concentrated again. Toluene and a saturated sodium bicarbonate solution were added to the resulting residue, and the insoluble matter was collected by filtration. The resulting powder was dried under reduced pressure to obtain 42.96 g of the title compound. The property values of the compound are as follows. 1H-NMR (CDCl3) delta (ppm): 2.30 (d, J=0.8Hz, 3H), 4.07 (s, 3H), 5.57 (brs, 1H), 5.68 (brs, 1H), 6.98 (brs, 1H), 7.00 (d, J=15.2Hz, 1H), 7.06 (d, J=7.6Hz, 1H), 7.54 (d, J=7.6Hz, 1H), 7.56 (d, J=15.2Hz, 1H), 7.82 (d, J=1.2Hz, 1H). ESI-MS; m/z 259 [M++H].

Reference： [1]Patent: EP2181992,2010,A1

65
[ 1123194-98-8 ]
[ 28689-14-7 ]
[ 3375-31-3 ]
[ 6163-58-2 ]
[ 1123197-79-4 ]

Yield	Reaction Conditions	Operation in experiment
87%	With N-ethyl-N,N-diisopropylamine; In water; N,N-dimethyl-formamide;	Synthesis of tert-Butyl 2-{(2E)-3-[6-methoxy-5-(4-methyl-1H-imidazol-1-yl)pyridin-2-yl]prop-2-enoyl}hydrazinecarboxylate DMF (52mL) was added to the 6-Bromo-2-methoxy-3-(4-methyl-1H-imidazol-1-yl)pyridine (13.0g, 48.5mmo1) and the tert-Butyl 2-acryloylhydrazinecarboxylate (9.9g, 53.3mmol) at room temperature under nitrogen atmosphere, And the mixture was stirred at 50C for 10minutes. Tri(o-tolyl)phosphine (885mg, 2.90mmol), Palladium (II) acetate (327mg, 1.45mmol) and N,N-diisopropylethylamine (12.7mL, 72.7mmol) were added to the mixture, and the reaction mixture was stirred at 100C for 4hours. The reaction mixture was cooled to room temperature and filtrated through Celite. The residue was washed twice with DMF (6mL). Water (104mL) was added dropwise to the filtrate at room temperature over 10minutes. The mixture was stirred at room temperature for 15hours. After the mixture was filtrated, the residue was washed with water/DMF =2:1(30mL) and MTBE (30mL). The obtained solid was suspended in MTBE (50mL) at room temperature for 2hours, filtrated and dried under the reduced pressure to obtain the title compound (15.8g, 87% yield). 1H-NMR (400MHz, CDCl3) delta (ppm):1.50 (s, 9H), 2.28 (d, J=1.2 Hz, 3H), 4.03 (s, 3H), 6.83 (brs, 1H), 6.97-7.02 (m, 3H), 7.51 (d, J=8.0 Hz, 1H), 7.59 (d, J=15.2 Hz, 1H), 7.82 (s, 1H), 8.01 (br s, 1H).

Reference： [1]Patent: EP2181992,2010,A1

66
aqueous potassium carbonate [ No CAS ]
[ 158063-67-3 ]
[ 6163-58-2 ]
[ 168267-99-0 ]
[ 1013647-67-0 ]