1,2-STEREOCONTROL AND 1,5-STEREOCONTROL IN 5-HEXENYL RADICAL CYCLIZATIONS - COOPERATIVE OR ANTAGONIST EFFECT - CONFRONTATION OF EXPERIMENTAL RESULTS WITH MM2 CALCULATIONS OF TRANSITION-STATES

被引：19

作者：

BERTRAND, MP ^{[1
]}

DERIGGI, I ^{[1
]}

LESUEUR, C ^{[1
]}

GASTALDI, S ^{[1
]}

NOUGUIER, R ^{[1
]}

JAIME, C ^{[1
]}

VIRGILI, A ^{[1
]}

机构：

[1] UNIV AUTONOMA BARCELONA,DEPT QUIM,E-08193 BARCELONA,SPAIN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 19期

关键词：

D O I：

10.1021/jo00124a012

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The cyclofunctionalization of 1,6-dienes 1 and 2 via the addition of tosyl radical allows the analysis of the combined effects of 1,2- and 1,5-stereocontrols on the outcome of 5-hexenyl radical cyclizations. MM2 calculations of transition states agree quite well with the experimental selectivity, i.e., exclusive 1,2-trans control, and predominance of 1,5-cis over 1,5-trans relationship. The addition of TsBr to carbohydrate-derived epimeric dienes 3a and 3b shows that the stereochemistry of the newly formed C-C bond is controlled by the configuration of the C2 center of the radical. 1,5-trans or 1,5-cis selectivity can be achieved depending on the configuration of C2.

引用

页码：6040 / 6045

页数：6

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