Alkylpalladium N-Heterocyclic Carbene Complexes: Synthesis, Reactivity, and Catalytic Properties

被引:33
作者
Esposito, Oriana [2 ]
Gois, Pedro M. P. [1 ,2 ,3 ]
Lewis, Alexandra K. de K. [1 ]
Caddick, Stephen [1 ]
Cloke, F. Geoffrey N. [2 ]
Hitchcock, Peter B. [2 ]
机构
[1] UCL, Dept Chem, London WC1H OAJ, England
[2] Univ Sussex, Sch Life Sci, Dept Chem & Biochem, Brighton BN1 9QJ, E Sussex, England
[3] Inst Super Tecn, CQFM, Dept Engn Quim & Biol, P-1049001 Lisbon, Portugal
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1021/om800455h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The dimers [trans-[(neopentyl)Pd(mu-Cl)(I(t)lBu)](2), 2, and (cis-[(neopentyl)Pd(mu-Cl)(IPr)](2), 3 ((IBu)-Bu-t = 1,3-bis-tert-butylimidazol-2-ylidene, IPr = 1,3-bis-2,6-diidopropylimidazol-2-ylidene), have been synthesized from [Pd(neopentyl)(Cl)(1,5-COD)], and their reactivity toward a variety of nucleophiles has been evaluated. In particular, this study revealed that 2 can be readily cleaved by primary and secondary amines, affording stable transamination products, which are surprisingly resistant to deprotonation. Dimer 3 was subsequently used as a catalyst in a series of Buchwald-Hartwig amination reactions of aryl chlorides.
引用
收藏
页码:6411 / 6418
页数:8
相关论文
共 62 条
[51]   Synthesis of the complexes [PdCIR(cod)] (R equals benzyl, ethyl; cod equals 1,5-cyclooctadiene). beta-elimination from [PdClEt(cod)] to give the eta(1),eta(2), and eta(3) isomers of [Pd-2(mu-Cl)(2)(C8H13)(2)] [J].
Stockland, RA ;
Anderson, GK ;
Rath, NP ;
BraddockWilking, J ;
Ellegood, JC .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1996, 74 (11) :1990-1997
[52]   Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995-1998 [J].
Suzuki, A .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 576 (1-2) :147-168
[53]   SELECTIVE CARBON-CARBON BOND FORMATION BY CROSS-COUPLING OF GRIGNARD-REAGENTS WITH ORGANIC HALIDES - CATALYSIS BY NICKEL-PHOSPHINE COMPLEXES [J].
TAMAO, K ;
SUMITANI, K ;
KUMADA, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (12) :4374-&
[54]   Ligands for palladium-catalyzed cross-couplings of alkyl halides: Use of an alkyldiaminophosphane expands the scope of the Stille reaction [J].
Tang, HF ;
Menzel, K ;
Fu, GC .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (41) :5079-5082
[55]   Unexpected reactivity of two-coordinate palladium-carbene complexes; synthetic and catalytic implications [J].
Titcomb, LR ;
Caddick, S ;
Cloke, FGN ;
Wilson, DJ ;
McKerrecher, D .
CHEMICAL COMMUNICATIONS, 2001, (15) :1388-1389
[56]  
Tsuji J., 1995, PALLADIUM REAGENTS C
[57]   High yielding alkylations of unactivated sp3 and sp2 centres with alkyl-9-BBN reagents using an NHC-based catalyst:: Pd-PEPPSI-IPr [J].
Valente, Cory ;
Baglione, Sylvia ;
Candito, David ;
O'Brien, Christopher J. ;
Organ, Michael G. .
CHEMICAL COMMUNICATIONS, 2008, (06) :735-737
[58]   Essays on organometallic chemistry.: Part 11.: N-heterocyclic carbenes:: state of the art in transition-metal-complex synthesis [J].
Weskamp, T ;
Böhm, VPW ;
Herrmann, WA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 600 (1-2) :12-22
[59]   Rational development of practical catalysts for aromatic carbon-nitrogen bond formation [J].
Wolfe, JP ;
Wagaw, S ;
Marcoux, JF ;
Buchwald, SL .
ACCOUNTS OF CHEMICAL RESEARCH, 1998, 31 (12) :805-818
[60]   Suzuki cross-couplings of unactivated secondary alkyl bromides and iodides [J].
Zhou, J ;
Fu, GC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (05) :1340-1341