Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study

被引：15

作者：

DiLabio, GA ^{[1
]}

Ingold, KU

Roydhouse, MD

Walton, JC

机构：

[1] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[2] CNR, Ottawa, ON K1A 0R6, Canada

[3] Natl Res Council Canada, Natl Inst Nanotechnol, Edmonton, AB T6G 2V4, Canada

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 23期

关键词：

D O I：

10.1021/ol0481683

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals gave distinct EPR spectra thanks to surprisingly large beta-hydrogen atom hyperfine splittings that enabled them to be characterized and monitored. DFT computations indicated that the axial species (X = CH2) had a higher barrier to rotation about the (O)C-alpha-C-beta bond. The computed difference DeltaHdegrees for the axial and equatorial radicals (R = H, X CH2) was 0.8 kcal mol(-1).

引用

页码：4319 / 4322

页数：4

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