Is phenyl a good migrating group in the rearrangement of organoborates generated from sulfur ylides?

Calculations show that the unexpected low phenyl migratory aptitude observed in reactions of mixed alkyl-aryl boranes with benzylic sulfur ylides can be attributed to (1) a conformational issue, (2) the reduction of the usual neighbouring effect of the phenyl in the transition state by the benzylic...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2006-02 (7), p.741-743
Main Authors: Robiette, Raphaël, Fang, Guang Yu, Harvey, Jeremy N, Aggarwal, Varinder K
Format: Article
Language:English
Subjects:
Alkanes - chemistry
Boron - chemistry
Hydrocarbons, Aromatic - chemistry
Models, Chemical
Organometallic Compounds - chemistry
Oxidation-Reduction
Stereoisomerism
Sulfur - chemistry
Thermodynamics
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Summary:Calculations show that the unexpected low phenyl migratory aptitude observed in reactions of mixed alkyl-aryl boranes with benzylic sulfur ylides can be attributed to (1) a conformational issue, (2) the reduction of the usual neighbouring effect of the phenyl in the transition state by the benzylic nature of the migrating terminus, (3) steric hindrance suffered by the larger phenyl group migrating to the hindered migrating terminus and this despite (4) the increase in the barrier to alkyl migration by the presence of a 'non-migrating' phenyl on the boron atom.
ISSN:1359-7345
1364-548X
DOI:10.1039/b514987h