The Heck reaction: mechanistic insights and novel ligands

被引:36
作者
Casey, M [1 ]
Lawless, J [1 ]
Shirran, C [1 ]
机构
[1] Natl Univ Ireland Univ Coll Dublin, Dept Chem, Dublin 4, Ireland
关键词
Heck reactions; palladium; phosphane; sulfane ligands; mechanism;
D O I
10.1016/S0277-5387(99)00398-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The kinetics of the Heck reaction of aryl iodides with methyl acrylate using phosphane ligands were studied. Triphenylphosphane strongly inhibited the reaction when used in excess over the Pd(0) precatalyst. The rate of reaction was found to be weakly dependent on the concentrations of both the aryl iodide and the alkene. The results indicate that the migratory insertion step is turnover limiting, with the oxidative addition to the aryl iodide being faster but not negligible. Phosphane sulfane hemilabile ligands were found to give good yields and good catalyst stability in Heck reactions. (C) 2000 Elsevier Science Ltd All rights reserved.
引用
收藏
页码:517 / 520
页数:4
相关论文
共 37 条
[1]   INTIMATE MECHANISM OF OXIDATIVE ADDITION TO ZEROVALENT PALLADIUM COMPLEXES IN THE PRESENCE OF HALIDE-IONS AND ITS RELEVANCE TO THE MECHANISM OF PALLADIUM-CATALYZED NUCLEOPHILIC SUBSTITUTIONS [J].
AMATORE, C ;
JUTAND, A ;
SUAREZ, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (21) :9531-9541
[2]   RATES AND MECHANISMS OF OXIDATIVE ADDITION TO ZEROVALENT PALLADIUM COMPLEXES GENERATED IN-SITU FROM MIXTURES OF PD0(DBA)2 AND TRIPHENYLPHOSPHINE [J].
AMATORE, C ;
JUTAND, A ;
KHALIL, F ;
MBARKI, MA ;
MOTTIER, L .
ORGANOMETALLICS, 1993, 12 (08) :3168-3178
[3]   RATES AND MECHANISM OF THE FORMATION OF ZEROVALENT PALLADIUM COMPLEXES FROM MIXTURES OF PD(OAC)(2) AND TERTIARY PHOSPHINES AND THEIR REACTIVITY IN OXIDATIVE ADDITIONS [J].
AMATORE, C ;
CARRE, E ;
JUTAND, A ;
MBARKI, MA .
ORGANOMETALLICS, 1995, 14 (04) :1818-1826
[4]   Mechanistic and kinetic studies of palladium catalytic systems [J].
Amatore, C ;
Jutand, A .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 576 (1-2) :254-278
[5]   Sulfur-imine mixed donor chelate ligands for asymmetric catalysis: enantioselective allylic alkylation [J].
Anderson, JC ;
James, DS ;
Mathias, JP .
TETRAHEDRON-ASYMMETRY, 1998, 9 (05) :753-756
[6]  
[Anonymous], REV HETEROATAOM CHEM
[7]   Catalytic asymmetric synthesis of quaternary carbon centers.: Exploratory studies of intramolecular Heck reactions of (Z)-α,β-unsaturated anilides and mechanistic investigations of asymmetric Heck reactions proceeding via neutral intermediates [J].
Ashimori, A ;
Bachand, B ;
Calter, MA ;
Govek, SP ;
Overman, LE ;
Poon, DJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (26) :6488-6499
[8]   A KINETIC INVESTIGATION OF SOME ELECTRONIC FACTORS AND LIGAND EFFECTS IN THE HECK REACTION WITH ALLYLIC ALCOHOLS [J].
BENHADDOU, R ;
CZERNECKI, S ;
VILLE, G ;
ZEGAR, A .
ORGANOMETALLICS, 1988, 7 (12) :2435-2439
[9]   PALLADIUM CATALYZED PHENYLATION OF ALLYLIC ALCOHOLS - DRAMATIC EFFECT OF TERTIARY-AMINES ON THE REACTION-RATE [J].
BENHADDOU, R ;
CZERNECKI, S ;
VILLE, G .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (04) :247-248
[10]   Syntheses of indoles via a palladium-catalyzed annulation between iodoanilines and ketones [J].
Chen, CY ;
Lieberman, DR ;
Larsen, RD ;
Verhoeven, TR ;
Reider, PJ .
JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (09) :2676-2677