THE BARRIERS TO TRIMETHYLSILYL MIGRATIONS IN INDENES AND BENZINDENES - SILATROPIC SHIFTS VIA AROMATIC TRANSITION-STATES

被引：31

作者：

RIGBY, SS ^{[1
]}

GUPTA, HK ^{[1
]}

WERSTIUK, NH ^{[1
]}

BAIN, AD ^{[1
]}

MCGLINCHEY, MJ ^{[1
]}

机构：

[1] MCMASTER UNIV,DEPT CHEM,HAMILTON,ON L8S 4M1,CANADA

来源：

POLYHEDRON | 1995年 / 14卷 / 19期

基金：

加拿大自然科学与工程研究理事会;

关键词：

D O I：

10.1016/0277-5387(95)00135-F

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The barriers to migration of a trimethylsilyl group around the five-membered ring of indene, and of linear and angular benzindenes, have been calculated at the unrestricted: Hartree-Fock (UHF) level of theory by using AMPAC and MOPAC. It Is found that the retention of aromatic character in the transition state and in the intermediate isoindene lowers the barrier for the silatropic shifts. A preliminary experimental study on a trimethysilyl derivative of angular benzindene reveals that Me(3)Si migration is indeed a facile process. However, in the corresponding bis-trimethylsilyl systems, rearrangements which require the intermediacy of geminal Me(3)Si groups have rather high barriers.

引用

页码：2787 / 2796

页数：10

共 27 条

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[23] Long-Range Chemical Ligation from N→N Acyl Migrations in Tryptophan Peptides via Cyclic Transition States of 10-to 18-Members
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[24] HYDROGEN TRANSITIONS BETWEEN (HF)(N) C-NH STRUCTURES (N=2-5) VIA D-NH TRANSITION-STATES AS MODELS FOR HYDROGEN TUNNELING IN HYDROGEN-FLUORIDE CLUSTERS
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[25] PHOTOCHEMICAL-REACTION OF N,N-DIALKYL BETA,GAMMA-UNSATURATED AMIDES - INTRAMOLECULAR HYDROGEN-TRANSFER REACTIONS OF ACYCLIC OLEFINS VIA 7-MEMBERED CYCLIC TRANSITION-STATES
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