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Synthesis and electrophilic cleavage of some verbenylstannanes
Journal article   Peer reviewed

Synthesis and electrophilic cleavage of some verbenylstannanes

David James Young and W Kitching
Journal of Organic Chemistry, Vol.50(21), pp.4098-4102
1985
url
https://doi.org/10.1021/jo00221a026View
Published Version

Abstract

trifluoroacetolysis
Trifluoroacetolysis of the allylic cis- and trans-verbenylstannanes yields a mixture of cis- and trans-δ-pinenes, confirming regiospecific γ-substitution. Analysis of the product distribution confirms the view that any inherent preference for γ-anti substitution (anti-SE′ process) is not so strong that steric effects on both reagent approach and product development cannot influence the balance between syn and anti stereocourses. Sulfur dioxide insertion (chloroform solvent) proceeds readily with the trans-stannane to provide the rearranged (tertiary) "δ-pinenylsulfinate" in a stereospecific syn fashion (syn-SE′ process). cis-Verbenylstannane is less reactive but is transformed to the same sulfinate. The verbenylstannanes were acquired by trimethyl- and triphenylstannylation (with (trimethyltin)lithium and (triphenyltin)lithium in tetrahydrofuran) of predominantly (∼90%) trans-verbenyl chloride. © 1985 American Chemical Society.

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