A comparison of monocyclic and bicyclic phospholanes as acyl-transfer catalysts

被引：60

作者：

Vedejs, E ^{[1
]}

Daugulis, O

Harper, LA

MacKay, JA

Powell, DR

机构：

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

[2] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 13期

关键词：

D O I：

10.1021/jo030007+

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis and evaluation of chiral phosphines 11, 15a, 19a, 24a, and 28a as nucleophilic catalysts for anhydride activation and kinetic resolution of alcohols is described. The relative reactivity follows the order 11a > 11b > 15a > 1 in the monocyclic series, and 24a > 19a > 28a in the bicyclic series, with an overall rate advantage of ca. 2 orders of magnitude for the bicyclic phospholanes over the monocyclic analogues. The increased reactivity of the bicyclic phospholanes for the acylation of alcohols is attributed to conformational effects and ground-state destabilization in a highly associative mechanism. Kinetic resolution data demonstrate promising enantioselectivities for 24a.

引用

页码：5020 / 5027

页数：8

共 68 条

[1]

[Anonymous], 1991, HETEROATOM CHEM

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