Stereoselective reactions of acyclic allylic phosphates with organocopper reagents

被引：37

作者：

Belelie, JL ^{[1
]}

Chong, JM ^{[1
]}

机构：

[1] Univ Waterloo, Dept Chem, Guelph Waterloo Ctr Grad Work Chem & Biochem GWC2, Waterloo, ON N2L 3G1, Canada

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2001年 / 66卷 / 16期

关键词：

D O I：

10.1021/jo0104431

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of acyclic allylic alcohols of general structure (RCH)-C-1=CHCH(OH)R-2 were resolved by Sharpless kinetic resolution. The hydroxyl groups of these enantiomerically enriched alcohols were derivatized to diethyl phosphates, and the derivatives were reacted with organocopper reagents. Cleanest substitution reactions were observed with reagents (R2CuCNLi2)-Cu-3. With R-1 = Me and R-3 = n-Bu, the size of R2 affected both the regioselectivity and stereoselectivity of the displacement. Larger R-2 groups gave higher regio- and stereoselectivities: with R-2 = 3-pentyl, > 98% S(N)2', regioselectivity and > 98% anti stereoselectivity were observed. Bn2CuCNLi2 gave stereoselectivities comparable to those observed with n-Bu2CuCNLi2 but t-Bu2CuCNLi2 exhibited much lower diastereofacial preference.

引用

页码：5552 / 5555

页数：4