STEREOCHEMISTRY OF RADICAL CYCLIZATIONS TO SIDE-CHAIN OLEFINIC BONDS - AN APPROACH TO CONTROL OF THE C-9 CENTER OF MORPHINE

被引：44

作者：

PARKER, KA

FOKAS, D

机构：

[1] Department of Chemistry, Brown University, Providence

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 14期

关键词：

D O I：

10.1021/jo00093a026

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Styrenes of general structure 5 undergo tandem radical cyclization to cis,cis-hydrophenanthrofurans 9, products which contain the carbocyclic skeleton of the morphine alkaloids. Vinylurethane 5E-NHCO(2)Et cyclizes to 9 alpha via the intermediate radical 7E-NHCO(2)Et in the chair-chair conformation. Cyclization of 5Z-NHCO(2)Et also gives predominantly 9 alpha instead of the expected 9 beta. This anomaly is attributed to the isomerization of 5Z to 5E at a rate competitive with that of cyclization.

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页码：3927 / 3932

页数：6

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