Cationic P(OPh)3- or PPh3-Rhodium(I) complex-catalyzed isomerizations of 5-alkynals to δ-alkynyl ketones, cyclopent-1-enyl ketones, and cyclohexenones

被引：16

作者：

Tanaka, Ken ^{[1
]}

Sasaki, Kaori ^{[1
]}

Takeishi, Kenzo ^{[1
]}

Hirano, Masao ^{[1
]}

机构：

[1] Tokyo Univ Agr & Technol, Grad Sch Engn, Dept Appl Chem, Koganei, Tokyo 1848588, Japan

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 2007卷 / 34期

关键词：

aldehydes; ketones; alkynes; rhodium; catalysis;

D O I：

10.1002/ejoc.200700550

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We have developed catalytic isomerizations of 5-alkynals to,gamma-alkynyl ketones and cyclopent-l-enyl ketones using [Rh{P(OPh)(3)}(2)jBF(4) as a catalyst. Cu(OTf)(2) and AgBF4 are also effective catalysts for the formation of gamma-alkynyl ketones. The substituents at the 4-positions in 5-alkynals play important roles in the selection of two different isomerization pathways. The first catalytic endo/trans hydroacylation of acyclic 5-alkynals leading to cyclohexenones was also developed with [Rh(PPh3)(2)]BF4 as a catalyst. Crossover deuterium-labeling studies indicated that these isomerization reactions proceed intramolecularly. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

引用

页码：5675 / 5685

页数：11