MM2 MODEL FOR THE INTRAMOLECULAR ADDITIONS OF ACYL-SUBSTITUTED RADICALS TO ALKENES

被引：41

作者：

BROEKER, JL ^{[1
]}

HOUK, KN ^{[1
]}

机构：

[1] UNIV CALIF LOS ANGELES,DEPT CHEM & BIOCHEM,LOS ANGELES,CA 90024

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 11期

关键词：

D O I：

10.1021/jo00011a038

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The modified MM2 force field devised earlier to calculate transition states for intramolecular radical additions (Spellmeyer, D. C.; Houk, K. N. J. Org. Chem. 1987, 52, 959) has been extended to include acyl-substituted radicals. Calculations of the regioselectivities and stereoselectivities of the radical cyclizations are in good agreement with experimental results. The calculations show that the C(acyl)-C(rad)...C(alkene) attack angle and the geometric preference for planarity of the C(O)CH2. radical, which is maintained in the transition structures for additions, cause the regioselectivities of acyl-substituted radical cyclizations to differ from those of alkyl radical cyclizations.

引用

页码：3651 / 3655

页数：5

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