Sensitive nature of ligand coupling and pseudorotation to electronic effect of substituent---ligand coupling in the reactions of benzylic aryl sulfoxides with benzylic Grignard reagents

doi:10.1016/S0040-4039(00)80517-1

Tetrahedron Letters

Volume 29, Issue 35, 1988, Pages 4441-4444

https://doi.org/10.1016/S0040-4039(00)80517-1 Get rights and content

Abstract

Unlike the reaction of benzylic 2-pyridyl sulfoxides with benzylic Grignard reagents, in the reaction of p-benzenesulfonylphenyl benzylic sulfoxides with benzylic Grignard reagents, benzylic groups bearing an electron-withdrawing group tends to couple with the aryl group preferentially. This change is considered to be due to a slight change of electronic environements which would effect on the ease of pseudorotation2) of the incipient σ-sulfurane formed during the reaction.

In the reaction of p-benzenesulfonylphenyl benzylic sulfoxides with benzylic Grignard reagents, benzylic groups bearing an electron-withdrawing group tends to couple with the aryl group preferentially.

References (5)

T. Kawai et al.
Phosphorus and Sulfur
(1987)

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^☆: see earlier paper of this series, S. Oae, T. Kawai, and N. Furukawa, Tetrahedron Lett., 25, 69 (1984); T. Kawai, N. Furukawa, and S. Oae, ibid., 25, 2549 (1984); S. Oae, Croat. Chem. Acta, 59, 129 (1986); S. Oae, Phosphorus and Sulfur, 27, 13 (1986); S. Oae, T. Kawai, N. Furukawa, and F. Iwasaki, J. Chem. Soc., Perkin Trans. 2, 1987, 405.

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Sensitive nature of ligand coupling and pseudorotation to electronic effect of substituent---ligand coupling in the reactions of benzylic aryl sulfoxides with benzylic Grignard reagents☆

Abstract

Phosphorus and Sulfur