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

Andrew J. Lucke, David J. Young

Research output: Contribution to journalArticlepeer-review


(Chemical Equation Presented) Cyclopropylmethyltrimethylstannanes undergo electrophilic cyclopropane cleavage in chloroform with simple inorganic electrophiles (H+, SO2, I2) in a homologous reaction to the SE′ cleavage of allylic stannanes. The σ-σ 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 σ-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 σ-σ 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.

Original languageEnglish
Pages (from-to)3579-3583
Number of pages5
JournalJournal of Organic Chemistry
Issue number9
Publication statusPublished - 29 Apr 2005
Externally publishedYes


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