Two Flavors of PEPPSI-IPr: Activation and Diffusion Control in a Single NHC-Ligated Pd Catalyst?

被引：54

作者：

Larrosa, Igor ^{[1
]}

Somoza, Clara ^{[1
]}

Banquy, Alexandre ^{[1
]}

Goldup, Stephen M. ^{[1
]}

机构：

[1] Queen Mary Univ London, Sch Biol & Chem Sci, London E1 4NS, England

来源：

ORGANIC LETTERS | 2011年 / 13卷 / 01期

基金：

英国工程与自然科学研究理事会;

关键词：

N-HETEROCYCLIC CARBENE; CROSS-COUPLING REACTIONS; DENSITY-FUNCTIONAL THEORY; ARYL CHLORIDES; OXIDATIVE ADDITION; SUZUKI POLYCONDENSATION; ARYLBORONIC ACIDS; ROOM-TEMPERATURE; PALLADIUM(0) COMPLEXES; HOMOGENEOUS CATALYSIS;

D O I：

10.1021/ol1027283

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Abnormal reactivity has been observed in Negishi, Suzuki Miyaura, and Kumada Tamao Corriu cross-couplings in which PEPPSI-IPr (where PEPPSI stands for pyridine enhanced precatalyst preparation, stabilization, and initiation and IPr refers to the NHC ligand) is employed, implicating the presence of two distinct Pd-0 species in the catalytic cycle. Polybrominated arenes and organometallic reagents react selectively to give the product of exhaustive polysubstitution regardless of the initial reaction stoichiometry. Competition experiments suggest that, after an initial activation controlled oxidative addition, reductive elimination produces an ultrareactive Pd-0 species which consumes all remaining C-Br bonds in the molecule under diffusion control.

引用

页码：146 / 149

页数：4

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