Electrophilic cleavage of cyclopropylmethystannanes: An experimental comparison of σ-σ and σ-π conjugation

A J Lucke; David James Young

doi:10.1021/jo047822p

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Electrophilic cleavage of cyclopropylmethystannanes: An experimental comparison of σ-σ and σ-π conjugation

Journal article

Peer reviewed

Electrophilic cleavage of cyclopropylmethystannanes: An experimental comparison of σ-σ and σ-π conjugation

A J Lucke and David James Young

Journal of Organic Chemistry, Vol.70(9), pp.3579-3583

2005

DOI: https://doi.org/10.1021/jo047822p

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Abstract

chemical analysis

chemical bonds

complexation

derivatives

fission reactions

spectroscopic analysis

(Chemical Equation Presented) Cyclopropylmethyltrimethylstannanes undergo electrophilic cyclopropane cleavage in chloroform with simple inorganic electrophiles (H+, SO2, I2) in a homologous reaction to the SEâ€² cleavage of allylic stannanes. The Ïƒ-Ïƒ conjugation between the carbon-tin bond and cyclopropane orbitals observed spectroscopically in the parent cyclopropylmethyltrimethylstannane is responsible for a rate enhancement of ca. 102 toward iodinolysis, relative to comparable alkyl stannanes. This acceleration is considerably less, however, than the ca. 109-fold rate enhancement provided by the corresponding Ïƒ-π conjugation in allylic stannanes. Methanol-tin coordination appears to reduce the activating influence of the metal, promoting methyl cleavage over cyclopropane fission with acid and iodine. Decreased Ïƒ-Ïƒ conjugation can also explain the decreased reactivity of cyclopropyltriphenylstannane compared with its trimethyltin counterpart. Cyclopropylmethylstannanes do not undergo the synthetically useful addition of aldehydes under conditions that facilitate the corresponding reaction of allylic stannanes. © 2005 American Chemical Society.

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Title: Electrophilic cleavage of cyclopropylmethystannanes: An experimental comparison of σ-σ and σ-π conjugation
Authors: A J Lucke (Author) - Griffith University
David James Young (Author) - Griffith University
Publication details: Journal of Organic Chemistry, Vol.70(9), pp.3579-3583
Publisher: American Chemical Society
Date published: 2005
DOI: 10.1021/jo047822p
ISSN: 0022-3263; 0022-3263
Organisation Unit: University of the Sunshine Coast, Queensland
Language: English
Record Identifier: 99449309302621
Output Type: Journal article

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