C(sp3)-N Bond-Forming Reductive Elimination of Amines: Reactions of Bisphosphine-Ligated Benzylpalladium(II) Diarylamido Complexes

被引:49
作者
Marquard, Seth L. [1 ]
Rosenfeld, Devon C. [1 ]
Hartwig, John F. [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
关键词
amido complexes; C-N bond formation; dissociation; palladium; reductive elimination; HETEROCYCLIC CARBENE COMPLEXES; OXIDATIVE-ADDITION; PALLADIUM; CARBON; REACTIVITY; HYDROAMINATION; VINYLARENES; AMINATION; MECHANISM; ANILINES;
D O I
10.1002/anie.200904032
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(Chemical Equation Presented) A rare event: The benzylpalladium amido complex 1 (Ar= napthyl) was used to study the mechanism of an unusual reductive elimination of amines (see scheme). The observed inversion of configuration is proposed to result from dissociation of the amido ligand, followed by nucleophilic attack on the benzylic carbon atom. binap = 2,2′- bis(diphenylphosphanyl)-1,1′-binaphthyl, dppf=1,1′- bis(diphenylphosphanyl)ferrocene. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:793 / 796
页数:4
相关论文
共 19 条
[1]   STEREOCHEMISTRY OF OXIDATIVE ADDITION OF BENZYL-ALPHA-D CHLORIDE AND BROMIDE TO "TRIS(TRIETHYLPHOSPHINE)PALLADIUM(0) - DIRECT OBSERVATION OF OPTICAL-ACTIVITY IN A CARBON-PALLADIUM SIGM-BONDED COMPLEX [J].
BECKER, Y ;
STILLE, JK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (03) :838-844
[2]   Carbon-nitrogen-bond-forming reductive elimination of arylamines from palladium(II) phosphine complexes [J].
Driver, MS ;
Hartwig, JF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (35) :8232-8245
[3]   Synthesis and reactivity of alkylpalladium N-heterocyclic carbene complexes [J].
Esposito, Oriana ;
Lewis, Alexandra K. de K. ;
Hitchcock, Peter B. ;
Caddick, Stephen ;
Cloke, F. Geoffrey N. .
CHEMICAL COMMUNICATIONS, 2007, (11) :1157-1159
[4]   Alkylpalladium N-Heterocyclic Carbene Complexes: Synthesis, Reactivity, and Catalytic Properties [J].
Esposito, Oriana ;
Gois, Pedro M. P. ;
Lewis, Alexandra K. de K. ;
Caddick, Stephen ;
Cloke, F. Geoffrey N. ;
Hitchcock, Peter B. .
ORGANOMETALLICS, 2008, 27 (24) :6411-6418
[5]  
HARTWIG JF, 2009, ORGANOTRANSITION MET, pCH8
[6]   Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl Halides [J].
Hartwig, John F. .
ACCOUNTS OF CHEMICAL RESEARCH, 2008, 41 (11) :1534-1544
[7]   Relative rates for the amination of η3-allyl and η3-benzyl complexes of palladium [J].
Johns, Adam M. ;
Tye, Jesse W. ;
Hartwig, John F. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (50) :16010-16011
[8]   A highly active palladium catalyst for intermolecular hydroamination. Factors that control reactivity and additions of functionalized anilines to dienes and vinylarenes [J].
Johns, AM ;
Utsunomiya, M ;
Incarvito, CD ;
Hartwig, JF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (06) :1828-1839
[9]   CARBON-NITROGEN BOND FORMATION BY REDUCTIVE ELIMINATION FROM NICKEL(II) AMIDO ALKYL COMPLEXES [J].
KOO, K ;
HILLHOUSE, GL .
ORGANOMETALLICS, 1995, 14 (09) :4421-4423
[10]   OXIDATIVE ADDITION OF BENZYL HALIDES TO ZERO-VALENT PALLADIUM COMPLEXES - INVERSION OF CONFIGURATION AT CARBON [J].
LAU, KSY ;
WONG, PK ;
STILLE, JK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (19) :5832-5840