THEORETICAL EXPLORATION OF THE PHOTO-CHEMICAL REARRANGEMENT OF OXAZIRIDINES

被引：44

作者：

OLIVEROS, E

RIVIERE, M

MALRIEU, JP

TEICHTEIL, C

机构：

[1] UNIV TOULOUSE 3,PHYS QUANT LAB,F-31077 TOULOUSE,FRANCE

[2] UNIV TOULOUSE 3,COMPOSES AZOTES POLYFONCT LAB,F-31077 TOULOUSE,FRANCE

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1979年 / 101卷 / 02期

关键词：

D O I：

10.1021/ja00496a007

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of the thermal and photochemical rearrangements of oxaziridines into amides has been explored through ab initio calculations using double-f plus diffuse basis sets and extensive CI. The lowest singlet excited state of the oxaziridinc ring results from an nπ→σ*o excitation and undergoes the breaking of the NO bond. The H(C) migration does not occur simultaneously; it should proceed on the ground state surface after deexcitation in the open geometry. The regioselectivity of the reaction would be due to an important barrier for the migration of the H atom in svn position with respect to the N lone pair. © 1979, American Chemical Society. All rights reserved.

引用

页码：318 / 322

页数：5

共 50 条

[1]

BEUGELMANS R, 1970, B SOC CHIM FR, P342

[2] DYNAMIC STEREOCHEMISTRY OF IMINES AND DERIVATIVES .7. THERMAL EPIMERIZATION OF CHIRAL OXAZIRIDINES [J].