An intramolecular titanium-catalyzed asymmetric Pauson-Khand type reaction

被引：118

作者：

Hicks, FA ^{[1
]}

Buchwald, SL ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1999年 / 121卷 / 30期

关键词：

D O I：

10.1021/ja990683m

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The development of the first catalytic asymmetric Pauson-Khand type cyclization of enynes is described. The active catalyst, (S,S)-(EBTHI)Ti(CO)(2) (1), is generated in situ from (S,S)-(EBTHI)TiMe2 (2). A variety of 1,6-enynes can be converted to the corresponding cyclopentenones in high yield (70-94%) with excellent ee's (87-96%). Limitations of the catalyst with respect to substrate structure are discussed. The absolute configurations of several of the enone products have been ascertained, and these assignments represent a reversal with respect to an assignment in the initial report. A rationale for the sense and levels of enantioselectivity for this catalyst is proposed.

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页码：7026 / 7033

页数：8

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