SYNTHETIC METHODS AND REACTIONS .146. OLEFINS FROM CROWDED CARBONYL-COMPOUNDS WITH TERT-BUTYLLITHIUM (TERT-BUTYLMAGNESIUM CHLORIDE) THIONYL CHLORIDE - STUDY OF CARBOCATIONIC REACTION INTERMEDIATES AND REARRANGEMENT CLEAVAGE UNDER STABLE ION CONDITIONS USING C-13 NMR-SPECTROSCOPY

被引：23

作者：

OLAH, GA ^{[1
]}

WU, AH ^{[1
]}

FAROOQ, O ^{[1
]}

PRAKASH, GKS ^{[1
]}

机构：

[1] UNIV SO CALIF,DEPT CHEM,LOS ANGELES,CA 90089

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 06期

关键词：

D O I：

10.1021/jo00293a023

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Crowded carbonyl compounds when reacted with iert-butyllithium or teri-butylmagnesium chloride followed by thionyl chloride treatment give in a one-pot reaction olefins in good to excellent yields. In the case of highly crowdedtertiary systems the reaction occurs either by rearrangement followed by the loss of a tert-butyl group (as isobutylene) or rearrangement accompanied by deprotonation, indicating the carbocationic nature of the process. The nature of intermediate carbocations and their cleavage-rearrangement process was probed in SbF5/SO2C1F solution of the corresponding alcohols under stable ion conditions using 13C NMR spectroscopy. © 1990, American Chemical Society. All rights reserved.

引用

页码：1792 / 1796

页数：5

共 22 条

[1]

[Anonymous], 1985, SUPERACIDS

[2] REMOTE SECONDARY DEUTERIUM KINETIC ISOTOPE EFFECTS AS A PROBE OF STERIC STRAIN IN THE SOLVOLYSIS OF TERTIARY ALKYL CARBINYL SYSTEMS [J].