Buchwald–Hartwig偶联反应

Buchwald–Hartwig 偶联反应是钯催化和碱存在下胺与卤代芳香化合物的交叉偶联反应。是合成芳胺的重要方法。百灵威可提供数量繁多种类齐全的Buchwald–Hartwig 相关试剂，部分产品备有国内现货。


◆ 发展历程：
Buchwald–Hartwig 这一类型的反应最早是由乌克兰的 Lev M. Yagupolskii 等在 1986 年发现的。此后美国的 Buchwald 和 Hartwig 两个团队又分别在 1994 年重新发现这个反应。耶鲁大学的 Hartwig 等用的是对溴甲苯与三丁基锡基胺之间的偶联。［1］


麻省理工学院的 Buchwald 等用的则是间溴苯甲醚与另一三丁基锡胺之间的偶联，见下。［2］


后来又发展了第二代的 Buchwald–Hartwig 反应，即用游离胺和强碱，代替最早使用的氨基锡烷。［3］


此外反应中的芳卤也可为拟芳卤三氟甲磺酸的酚酯所代替。胺可为伯胺或仲胺，胺上的取代基可以为任何有机基团。钯催化剂常为钯磷配合物，如四( 三苯基膦) 钯，也可为三( 双亚苄基丙酮)二钯［4］等其他钯配合物。反应用碱一般为双( 三甲硅基)氨基钠或叔丁醇盐。

◆ 相关产品：
产品编号 名称与规则 包装* 目录价*
46-3000 Tris(dibenzylideneacetone)dipalladium(0)
三(双亚苄基丙酮)双钯 500mg 745
1g 845
811200 1,1'-Bis(diphenylphosphino)ferrocene palladium(II)chloride
1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 1g 270
5g 1013
411434
46-0400 Dichlorobis(benzonitrile)palladium (II)
二(苯腈)二氯化钯(II) 250 mg 200
1g 545
5g 2043
46-1780
46-1781 Palladium(II) acetate
乙酸钯 1g 873
2g 1616
5g 2820
182482
46-2150 Tetrakis(triphenylphosphine)palladium(0)
四(三苯基膦)钯 1g 200
5g 745
25g 2800
205985
26-0270 1,1'-Bis(diphenylphosphino)ferrocene DPPF
1,1'-双(二苯基膦)二茂铁 1g 234
5g 518
25g 1943
102357
15-8050 Tri-o-tolylphosphine
三(邻-甲苯基)膦 1g 200
5g 400
25g 980
15-1045 2-(Di-t-butylphosphino)biphenyl,99%JohnPhos
2-（二叔丁基磷）联苯 500mg 585
2g 1755
15-1140 2-(Dicyclohexylphosphino)biphenyl
2-（二环己基磷）联苯 500mg 345
2g 1035
15-1145 2-Dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl
2-二环己基磷-2-（N,N-二甲基氨基）联苯 500mg 600
2g 1800
07-0299 1,3-Bis(2,4,6-trimethylphenyl)imidazolium chloride
1,3-双(2,4,6-三甲基苯基)氯化咪唑 1g 690
5g 2760


*包装：仅列出部分包装，更多包装情况请联系百灵威。
*目录价：价格供参考，购买前请联系百灵威核实销售价格。

◆ 参考资料：
1.Frederic Paul, Joe Patt, John F. Hartwig (1994), "Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides", J. Am. Chem.Soc. 116 (13): 5969–5970.
2.Anil S. Guram and Stephen L. Buchwald (1994), "Palladium-Catalyzed Aromatic Aminations with in situ Generated Aminostannanes", J. Am. Chem. Soc. 116 (17): 7901–7902.
3.Janis Louie and John F. Hartwig (1995), "Palladium-catalyzed synthesis of arylamines from aryl halides. Mechanistic studies lead to coupling in the absence of tin reagents", Tetrahedron Letters 36 (21): 3609–3612.
4.John P. Wolfe and Stephen L. Buchwald (2004). "Palladium-Catalyzed Amination Of Aryl Halides And Aryl Triflates". Org. Synth.; Coll. Vol. 10: 423.
◆ 最新产品：
Buchwald Biaryl Phosphine Ligand Kit
for Aromatic Carbon-Heteroatom Formation, Suzuki Coupling and Negishi Cross-coupling




96-5500 Buchwald Biaryl Phosphine Ligand Kit for Aromatic Carbon-Heteroatom Formation, Suzuki Coupling and Negishi Cross-coupling Contains the smallest unit size of the sixteen compounds listed 1 kit
15-1043 racemic-2-Di-t-butylphosphino-1,1'-binaphthyl, 98% [255836-67-0] P; FW: 398.53; white xtl.; m.p. 147-149 250mg
1g
Technical Notes:
1. Ligand for the Pd-catalyzed formation of oxygen heterocycles.
2. Ligand for the intermolecular Pd-catalyzed synthesis of aryl ethers.
3. Ligand for the intramolecular Pd-catalyzed synthesis of aryl ethers.
4. Ligand for the synthesis of carbazoles by Pd-catalyzed double N-arylation reaction.
5. Ligand fo the Pd-catalyzed cyanation of (hetero)arylchlorides.

References:
1. J. Am. Chem. Soc., 2000, 122, 12907.
2. J. Am. Chem. Soc., 2001, 123, 10770.
3. J. Am. Chem. Soc., 2001, 123, 12202.
4, Tetrahedron, 2006, 62, 6792.
5. Org. Lett., 2007, 9, 1711.
15-1045 2-(Di-t-butylphosphino)biphenyl, 99% JohnPhos [224311-51-7] C20H27P; FW: 298.41; colorless xtl.; m.p. 85/ 500mg 10g
2g 50g
Technical Notes:
1. Ligand used in the palladium-catalyzed synthesis of aromatic amines from aryl chlorides, bromides and triflates.
2. Ligand employed in a very active and general catalyst for Suzuki coupling reactions using aryl chlorides,bromides and triflates.
3. Ligand for the palladium-catalyzed formation of diarylethers from aryl chlorides and bromides.
4. Ligand used in palladium-catalyzed synthesis of oxindoles from " -chloroacetanilides.
5. Effective ligand used in palladium-catalyzed arylation of thiazoles.
6. Used in the formation of 2-benzylindolines via sequential palladium-catalyzed N-arylation/cyclization/C-arylation.
7. Selective in the palladium-catalyzed arylation of silyl enol ethers formed from copper-catalyzed reduction of enones.
8. Ligand used in the palladium-catalyzed vinylation of aryl bromides.
9. Ligand used in the platinum-catalyzed synthesis of indolizinones.
10. Ligand used in the palladium-catalyzed diarylation of thiophenes.
11. Ligand used in the amination of vinyl halides by carbazates.
12. Ligand used in the regeioselective synthesis of 2,4-disubstituted syloles.



References:
1. Angew. Chem. Int. Ed., 1999, 38, 2413. 8. Org. Lett., 2004, 6, 4809.
2. J. Org. Chem., 2000, 65, 1158. 9. Org. Lett., 2006, 7, 63.
3. J. Am. Chem. Soc., 1999, 121, 9550. 10.Org. Lett., 2007, 9, 1169.
4. J. Am. Chem. Soc., 1999, 121, 4369. 11.J. Org. Chem., 2006, 71, 8309.
5. J. Am. Chem. Soc., 2003, 125, 12084. 12. Org. Lett., 2007, 9, 275.
6. Tetrahedron, 2003, 59, 5685. 13. J. Am. Chem. Soc., 2008, 130, 1526.
7. J. Am. Chem. Soc., 2004, 126, 13906.
15-1048 Di-t-butylphosphino-2'-(N,N-dimethylamino)biphenyl, 98% [224311-49-3]
(CH3)2NC6H4C6H4P(C4H9)2; FW: 341.47; white xtl. 500mg
2g
Technical Notes:
1. Useful ligand for Pd-catalyzed carbon-oxygen bond forming reactions.
2. Ligand used selective Pd-catalyzed arylation of ammonia.
3. Ligand used for selective Pd-catalyzed silylation of aryl chlorides.

References:
1. J. Am. Chem. Soc., 2001, 123, 12202.
2. J. Am. Chem. Soc., 2007, 129, 10354.
3. Org. Lett., 2007, 9, 3785.
15-1049 2-Di-t-butylphosphino-2'-methylbiphenyl, 99% [255837-19-5]
C21H29P; FW: 312.43; white xtl.
Technical Notes:
1. Ligand used in the Pd-catalyzed arylations of malonate esters and 1,3-diketones.
2. Ligand used in the Pd-catalyzed formation of t-butyl ethers from unactivated aryl halides.
3. Ligand used in the Pd-catalyzed " -arylations of nitroalkanes.

References:
1. J. Am. Chem. Soc., 2000, 122, 1360.
2. J. Org. Chem., 2001, 66, 2498.
3. J. Org. Chem., 2002, 67, 106.
15-1051 2-Di-t-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-tri-i-propylbiphenyl, min. 98% [857356-94-6] C33H53P; FW: 480.75; white microxtl.; m.p. 166-168/ 250mg
1g
Technical Notes:
1. Ligand for the palladium-catalyzed amidation of aryl chlorides.
2. Ligand for the palladium-catalyzed synthesis of phenols from aryl halides.
3. Ligand for the palladium-catalyzed coupling of aryl halides and secondary alcohols.

References:
1. J. Am. Chem. Soc., 2007, 129, 13001.
2. J. Am. Chem. Soc., 2006, 128, 10894.
3. J. Am. Chem. Soc., 2005, 127, 8146.
15-1052 2-Di-t-butylphosphino-2',4',6'-tri-i-propyl-1,1'-biphenyl, min. 98% t-butylXPhos [564483-19-8] C29H45P; FW: 424.64; white xtl.; m.p. 147-149/ 500mg
2g
Technical Notes:
1. Ligand for the Pd-catalyzed synthesis of phenols and aromatic ethers.
2. Ligand for the Pd-catalyzed N-arylation of aminoheterocycles.
3. Ligand for the Pd-catalyzed N-arylation of indazoles and pyrazoles.
4. Ligand for the Pd-catalyzed amination of aryl nonaflates.
5. Ligand for the Pd-catalyzed stereoselective formation of alfa-O-glycosides.
6. See 15-1149 Technical Note 3.

References:
1. J. Am. Chem. Soc., 2006, 128, 10694. 3. J. Org. Chem., 2006, 71, 430.
2. Angew. Chem. Int. Ed., 2006, 45. 4.O rg. Lett., 2007, 9, 3173.
15-1140 2-(Dicyclohexylphosphino)biphenyl, 98% [247940-06-3] C12H9[P(C6H11)2]; FW: 350.49; white xtl.; m.p. 103/ 500mg 10g
2g 50g
Technical Notes:
1. See 15-1045.
2. Ligand used in the palladium-catalyzed sy nthesis of aromatic amines from aryl chlorides, bromides and triflates.
3. Ligand employed in Suzuki coupling reactions in volving aryl chlorides, bromides and triflates.
4. Useful ligand for the Pd-catal yzed oxidation of alcohols in the presence of chlorobenzenes.
5. Useful ligand for the Pd-catalyzed amination with ammonia equivalents.
6. Ligand for the gold(I)-catalyzed intramolecular [4+2] cycl oadditions involving 1,3-enynes and arylalkynes with alkenes.
7. Ligand used in the palladium-catalyz ed borylation of aryl bromdies.
8. Ligand used in the palladium-catalyz ed siliylation of aryl chlorides.

References:
1. Angew. Chem. Int. Ed., 1999, 38, 2413. 5. Org. Lett., 2001, 3, 3417.
2. J. Org. Chem., 2000, 65, 1158. 6. J. Am. Chem. Soc., 2005, 127, 6178.
3. J. Am. Chem. Soc., 1999, 121, 9550. 7. Helv. Chim. Acta., 2006, 89, 936.
4. Org. Lett., 2003, 5, 2485. 8. Org. Lett,, 2007, 9, 3785.
15-1142 2'-Dicyclohexylphosphino-2,6-dimethoxy-3-sulfonato-1,1'-biphenyl hydrate sodium salt, min. 98% C26H34NaO5PS.XH2O; FW: 512.58; light yellow solid
Note: Soluble version of 15-1143 S-Phos. 500mg
2g
Technical Note:
1. First general ligand for the Pd-catalyzed Suzuki-Miyaura coupling reaction of aryl chlorides and for the coupling of challenging substrate combinations in water.

15-1143 2-Dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, min. 98% S-Phos C26H35O2P; FW: 410.53; white xtl.; m.p. 158-162/ 500mg
2g
Technical Notes:
1. Ligand used in the palladium-catalyzed Suzuki-Miyaura coupling of boronic esters with heteroaryl halides.
2. Ligand used in the palladium-catalyzed Suzuki-Miyaura coupling of boronic acids with aryl halides
3. Suzuki-Miyaura coupling of potassium aryl trifluoroborates with aryl chloride.
4. Employed in the gold(I)-catalyzed intramolecular [4+2] cycloadditions of 1,3-enynes and arylalkynes with alkenes.
5. Effictive ligand in the palladium-catalyzed amination of heteroaryl halides.
6. Ligand employed in borylation of aryl chlorides.
7. Ligand used in palladium-catalyzed Kumada-Corriu cross coupling at low temperatures.


References:
1. J. Am. Chem. Soc., 2004, 126, 706.
2. Angew Chem. Int. Ed., 2004, 43, 1871.
3. Org. Lett., 2004, 6, 2649.
4. J. Am. Chem. Soc., 2005, 127, 6178.
5. Org. Lett., 2005, 7, 3965.
6. Angew. Chem. Int. Ed, 2007, 46, 5359.
7. J. Am. Chem. Soc., 2008, 129, 3844.
15-1145 2-Dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 98% DavePhos [213697-53-1]
(CH3)2NC6H4-C6H4P(C6H11)2; FW: 393.55; white xtl.; m.p.115-119/ 500mg
2g
Technical Notes:
1. Ligand used in the palladium-catalyzed Suzuki coupling and amination of unactivated aryl chlorides. The reactions generally occur at room temperature and give high yields of product.
2. Ligand used in palladium-catalyzed C-N bond formation. A general synthesis of N6-aryl-2'-deoxyadenosine analogues.
3. Ligand used in palladium-catalyzed N-arylation of indoles.
4. Ligand used in palladium-catalyzed synthesis of aryl-tert-butyl ethers.
5. Effective ligand in the palladium-catalyzed arylation of ester enolates.
6. Ligand employed in arylation of ketone enolates using ortho-halo nitrobenzenes.
7. Ligand employed in the amination of aryl nonaflates using palladium catalysts.
8. Ligand used for cascade alkenyl amination/Heck reaction for the synthesis of indoles.
9. Ligand used in palladium-catalyzed Kumada-Corriu cross coupling at low temperatures.
10. Ligand used in rhodium-catalyzed intramolecular hydroamination of unactivated terminal and internal alkenes with primary and secondary amines.


15-1145
(cont.)
2-Dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 98% DavePhos [213697-53-1]

References:
1. J. Am. Chem. Soc., 1998, 120, 9722. 6. J. Am. Chem. Soc., 2002, 124, 15168.
2. J. Am. Chem. Soc., 1999, 121, 6090. 7. J. Org. Chem., 2003, 68, 9563.
3. Org. Lett., 2000, 2, 1403. 8. Chem. Eur. J., 2005, 11, 2276.
4. J. Org. Chem., 2001, 66, 2498. 9. J. Am. Chem. Soc., 2007, 129, 3844.
5. J. Am. Chem. Soc., 2001, 123, 7996. 10. J. Am. Chem. Soc., 2008, 130, 1570.
15-1146 2-Dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl, min. 98% RuPhos [787618-22-8]
C30H43O2P; FW: 466.64; white pwdr.; m.p. 123-124/ 500mg
2g
Technical Notes:
1. Ligand used for the Pd-catalyzed Negishi cross-coupling reaction of (hetero)arylchlorides.
2. Ligand used for the Pd-catalyzed synthesis of N-aryl benzimidazoles.
3. Ligand used for the Pd-catalyzed synthesis of heteroacenes.

References:
1. J. Am. Chem. Soc., 2004, 126, 13028.
2. Angew. Chem. Int. Ed., 2007, 46, 7509.
3. J. Org. Chem., 2007, 72, 5119.
15-1135 2'-Dicyclohexylphosphino-2,6-di-i-propyl-4-sulfonato-1,1'-biphenyl hydrate sodium salt [870245-84-4]
C30H42NaO3PS; FW: 536.88; white solid 500mg
2g
Technical Notes:
1. Water soluble catalyst for Sonogashira coupling reactions.
2. Water soluble catalyst for couplings of benzyl chlorides and terminal alkynes.

References:
1. Angew. Chem. Int. Ed., 2005, 44, 6173.
2. Synlett 2006, 2941.
15-1148 2-Dicyclohexylphosphino-2'-methylbiphenyl, min. 98% MePhos [251320-86-2]
C25H33P; FW: 364.51; white xtl.; m.p. 107-110/ 500mg
2g
Technical Notes:
1. Ligand for the Pd-catalyzed formation of " -arylketones.
2. Ligand for the Pd-catalyzed amination reaction (See 15-1045).
3. Ligand for the Pd-catalyzed hydrazone arylation.

References:
1. J. Am. Chem. Soc., 2000, 122, 1360.
2. Adv. Synth. Catal., 2005, 347, 773.
15-1149 2-Dicyclohexylphosphino-2',4',6'-tri-i-propyl-1,1'-biphenyl, min. 98% X-Phos [564483-18-7]
C33H49P; FW: 476.72; white pwdr,; m.p. 185/ 500mg
2g
Technical Notes:
1. Exceptional ligand for Pd-catalyzed amination and amidation of aryl sulfonates.
2. Ligand used for the Pd-catalyzed Suzuki-Miyaura coupling reaction and carbonyl enolate coupling.
3. Ligand used for the chemoselective amination of arylchlorides.
4. Ligand used for the Pd-catalyzed borylation of aryl chlorides.
5. Ligand used for the Pd-catalyzed amination of vinyl halides and triflates.
6. Ligand used for the Pd-catalyzed three-component synthesis od indoles.

References:
1. J. Am. Chem. Soc., 2003, 125, 6653. 5. Angew. Chem. Int. Ed., 2007, 46, 5359.
2. J. Am. Chem. Soc., 2003, 125, 11818. 6. J. Org. Chem., 2005, 70, 8638.
3. Angew. Chem. Int. Ed., 2006, 45, 6523. 7. Angew. Chem. Int. Ed., 2007, 46, 1529.
4. J. Am. Chem. Soc., 2007, 129, 3358.
15-1152 2-(Dicyclohexylphosphino)-3,6-dimethoxy-2'-4'-6'-tri-i-propyl-1,1'-biphenyl, min. 98% BrettPhos
C35H53O2P; FW: 536.77; white xtl.; m.p. 191-193/ 250mg
1g
Technical Notes:
1. Catalyst for cross-coupling reactions using aryl mesylates with electron-deficient anilines.
2. Catalyst for rapid C-N bond-forming process at low catalyst loading.

Reference:
1. J. Am. Chem. Soc., 2008, 130, 13552.
15-1745 2-Diphenylphosphino-2'-(N,N-dimethylamino)biphenyl, 98% [240417-00-9]
C26H24NP; FW: 381.46; white pwdr. 500mg
2g
Technical Notes:
1. Useful ligand for sterically hindered substrates in the Pd-catalyzed amination reactions of aryl bromides.
2. Ligand employed in the coupling of enantiomerically pure cis-dimethylpiperazine with bromobenzene . Epimerization was not observed.
3. Ligand employed for the Pd-catalyzed heteroarylation of acetone.

References:
1. J. Am. Chem. Soc., 2001, 123, 1792.
2. Tetrahedron Lett., 2003, 44, 8869.


Buchwald Palladacycle Precatalyst Kit

96-5503 Buchwald Palladacycle Precatalyst Kit 1kit
Contains the smallest unit of the items listed below. Components available for individual sale.
46-0264 Chloro(2-di-t-butylphosphino-2',4',6'-tri-i-propyl-1,1'-biphenyl)[2-(2-aminoethyl)phenyl] palladium(II), min. 98% C37H55ClNPPd; FW: 686.69; white pwdr.
Technical Note:
1. See 46-0268. 100mg
500mg
46-0269 Chloro(2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-bipTechnical
Note:1. See 46-0268.henyl)[2-(2-aminoethylphenyl)]palladium(II) dichloromethane adduct, min. 98% [1028206-58-7]
C34H45ClNO2PPd; FW: 672.57; white pwdr.
Technical Note:
1. See 46-0268. 250mg
1g
46-0267 Chloro[2-(dicyclohexylphosphino)-3,6-dimethoxy-2'-4'-6'-tri-i-propyl-1,1'-biphenyl][2-(2-aminoethyl)phenyl] palladium(II), min. 98%
C43H63ClNO2PPd; FW: 798.81; white pwdr. 100mg
500mg
Technical Notes:
1.Catalyst for cross-coupling reactions using aryl mesylates with electron-deficient anilines.
2. Catalyst for rapid C-N bond-forming process at low catalyst loading.

46-0266 Chloro(2-dicyclohexylphosphino-2',6'-di-i-propoxy-1,1'-biphenyl)[2-(2-aminoethylphenyl)]palladium(II), methyl-t-butylether adduct, min. 98% [1028206-60-1]
C38H53ClNO2PPd; FW: 728.68; white pwdr.

Technical Note:
1. See 46-0268. 100mg
500mg
46-0268 Chloro(2-dicyclohexylphosphino-2',4',6'-tri-i-propyl-1,1'-biphenyl)[2-(2-aminoethyl)phenyl] palladium(II) methyl-t-butylether adduct, min. 98% [1028206-56-5]
C41H59ClNPPd; FW: 738.76; white pwdr. 250mg
1g
Technical Notes:
1. Catalyst for cross-coupling reactions of electron-deficient anilines with aryl chlorides.
2. Catalyst for rapid C-N bond-forming process at low catalyst loading.
3. Catalyst for C-N cross-coupling reactions, at or below room temperature.

Reference:
1. J. Am. Chem. Soc., 2008, 130, 6686.