Is phenyl a good migrating group in the rearrangement of organoborates generated from sulfur ylides?
- 5 January 2006
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Chemical Communications
- No. 7,p. 741-743
- https://doi.org/10.1039/b514987h
Abstract
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.Keywords
This publication has 26 references indexed in Scilit:
- Synthesis and Applications of Chiral Organoboranes Generated from Sulfonium YlidesJournal of the American Chemical Society, 2005
- α-Halo boronic esters in asymmetric synthesisTetrahedron, 1998
- Theoretical study of the reaction mechanism and migratory aptitude of the pinacol rearrangementJournal of the American Chemical Society, 1993
- Theoretical study on the migratory aptitude in pinacol rearrangementTetrahedron Letters, 1990
- Organoboranes for synthesis. 7. An improved general synthesis of primary amines from alkenes via hydroboration-organoborane chemistryTetrahedron, 1987
- Facile redistribution of trialkylboranes with aryl borates. General synthesis of dialkylborinic acids and estersJournal of the American Chemical Society, 1971
- Reaction of organoboranes with ethyl bromoacetate and ethyl dibromoacetate under the influence of potassium 2,6-Di-tert-butylphenoxide, an unusual base with large steric requirementsJournal of the American Chemical Society, 1969
- Reaction of organoboranes with chloroacetonitrile under the influence of potassium 2,6-Di-tert-butylphenoxide. A convenient procedure for the conversion of olefins into nitriles via hydroborationJournal of the American Chemical Society, 1969
- Reaction of organoboranes with bromoacetone under the influence of potassium 2,6-Di-tert-butylphenoxide. A convenient procedure for the conversion of olefins into methyl ketones via hydroborationJournal of the American Chemical Society, 1969
- The reaction of B-vinylic- and B-alkyl-9-borabicyclo[3.3.1]nonane derivatives with ethyl diazoacetate and diazoacetoneTetrahedron Letters, 1969