Electronic effects on the selectivity of Pd-catalyzed C-N bond-forming reactions using biarylphosphine ligands: The competitive roles of amine binding and acidity

被引：92

作者：

Biscoe, Mark R. ^{[1
]}

Barder, Timothy E. ^{[1
]}

Buchwald, Stephen L. ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 38期

关键词：

amination; chemoselectivity; homogeneous catalysis; palladium; phosphanes;

D O I：

10.1002/anie.200702122

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Electronic influence: Correlation between the relative binding constants of amines to isolated [SPhosPd(Ph)C;] (SPhos = 2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl) and the pKa of the amine complexes shows that the selectivity in the catalytic arylation of amines is influenced by the electronic properties of the amine. Selectivities observed in C-N cross-coupling reactions using neutral amines can be reversed using lithium amides. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

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页码：7232 / 7235

页数：4

相关论文

共 19 条

[1]

Albert A., 1984, DETERMINATION IONIZA

[2] Cyclometallation of 2-phenylaniline and (R)-alpha-methylbenylamine by palladium(II) acetate. X-ray molecular structure of [Pd{2-(2'-NH2C6H4)C6H4}Br(PPh(3))] [J].

Albert, J ;

Granell, J ;

Luque, A ;

Minguez, J ;

Moragas, R ;

FontBardia, M ;

Solans, X .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 522 (01) :87-95

[3] Mechanistic studies on oxidative addition of aryl halides and triflates to Pd(BINAP)2 and structural characterization of the product from aryl triflate addition in the presence of amine [J].

Alcazar-Roman, LM ;

Hartwig, JF .

ORGANOMETALLICS, 2002, 21 (03) :491-502

[4]

[Anonymous], UNPUB

[5] Structural insights into active catalyst structures and oxidative addition to (biaryl)phosphine - Palladium complexes via density functional theory and experimental studies [J].

Barder, Timothy E. ;

Biscoe, Mark R. ;

Buchwald, Stephen L. .

ORGANOMETALLICS, 2007, 26 (09) :2183-2192

[6] Palladium-catalyzed arylation of linear and cyclic polyamines [J].

Beletskaya, IP ;

Averin, AD .

PURE AND APPLIED CHEMISTRY, 2004, 76 (09) :1605-1619

[7]

BROWN HC, 1955, DETERMINATION ORGANI

[8] Palladium-mediated N-arylation of heterocyclic diamines: Insights into the origin of an unusual chemoselectivity [J].

Cabello-Sanchez, Noemi ;

Jean, Ludovic ;

Maddaluno, Jacques ;

Lasne, Marie-Claire ;

Rouden, Jacques .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (06) :2030-2039

[9] DIMETHYL(N,N,N',N'-TETRAMETHYLETHANEDIAMINE)PALLADIUM(II) AND DIMETHYL[1,2-BIS(DIMETHYLPHOSPHINO)ETHANE]PALLADIUM(II) - SYNTHESES, X-RAY CRYSTAL-STRUCTURES, AND THERMOLYSIS, OXIDATIVE-ADDITION, AND LIGAND-EXCHANGE REACTIONS [J].

DEGRAAF, W ;

BOERSMA, J ;

SMEETS, WJJ ;

SPEK, AL ;

VANKOTEN, G .

ORGANOMETALLICS, 1989, 8 (12) :2907-2917

[10]

Hartwig, 2002, Handbook of Organopalladium Chemistry for Organic Synthesis, P1051, DOI [DOI 10.1002/0471212466.CH42, 10.1002/0471212466.ch42]