Tandem enyne metathesis and Claisen rearrangement: A versatile approach to conjugated dienes of variable substitution patterns

被引：42

作者：

Clark, Daniel A. ^{[1
]}

Kulkarni, Amol A. ^{[1
]}

Kalbarczyk, Kyle ^{[1
]}

Schertzer, Bryan ^{[1
]}

Diver, Steven T. ^{[1
]}

机构：

[1] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 49期

关键词：

D O I：

10.1021/ja063132m

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

To extend the versatility of the ruthenium carbene-promoted enyne metathesis, it was combined with an Ireland ester enolate Claisen rearrangement. This reaction sequence provided conjugated dienes of higher substitution pattern than that obtained through a cross-enyne metathesis alone. The Ireland-Claisen was conducted across both acyclic and cyclic dienes produced from cross-metathesis and methylene-free enyne metathesis, respectively. In the case of cyclodienes, the Ireland-Claisen rearrangement produced s-trans locked dienes which underwent mode-selective ene reaction. The tandem, sequential use of the Ireland-Claisen rearrangement also proved suitable for chirality transfer originating from chiral propargylic alcohols. Last, the tandem metathesis/Ireland-Claisen was utilized to access 4-substituted3,5-cyclohexadiene diol derivatives, which are valuable chiral intermediates for natural product synthesis. The combination of this pericyclic reaction with a catalytic metathesis reaction extends the versatility of cross-metathesis since additional diene motifs can be accessed.

引用

页码：15632 / 15636

页数：5

共 51 条

[1] The nitroso ene reaction: A regioselective and stereoselective allylic nitrogen functionalization of mechanistic delight and synthetic potential [J].