Palladium (II/IV) catalyzed cyclopropanation reactions: scope and mechanism

被引：49

作者：

Lyons, Thomas W. ^{[1
]}

Sanford, Melanie S. ^{[1
]}

机构：

[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

来源：

TETRAHEDRON | 2009年 / 65卷 / 16期

关键词：

ANION CAPTURE PROCESSES; O BOND FORMATION; (Z)-4'-ACETOXY-2'-BUTENYL 2-ALKYNOATES; INTRAMOLECULAR CYCLOPROPANATION; CYCLIZATION-CYCLOPROPANATION; GAMMA-BUTYROLACTONES; EFFICIENT SYNTHESIS; ACID-DERIVATIVES; ALKENES; CYCLOISOMERIZATION;

D O I：

10.1016/j.tet.2008.10.107

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

This report describes detailed studies of the scope and mechanism of a new Pd-catalyzed oxidation reaction for the stereospecific conversion of enynes into cyclopropyl ketones. Unlike related Pd-II/O, Au and Pt-catalyzed cyclopropane-forming reactions, these transformations proceed with net inversion of geometry with respect to the starting alkene. This result, along with other mechanistic data, is consistent with a Pd-II/IV mechanism in which the key cycloptopane-forming step involves nucleophilic attack of a tethered olefin onto a Pd-IV-C bond. (C) 2008 Elsevier Ltd. All rights reserved.

引用

页码：3211 / 3221

页数：11

共 63 条

[1] Palladium-catalyzed ring-forming aminoacetoxylation of alkenes [J].