Unexpected reactions of Grignard reagents with selected β-carboalkoxy substituted sulfinate esters

A series of six-membered rings bearing cis oriented vicinal carboxylate and sulfinate esters were treated with Grignard reagents with the intention of transforming them to beta-carboalkoxy substituted sulfoxides. The expected outcome did not transpire and instead the substrates demonstrated the capacity to accept 3 equiv. of organometallic agent in an uncontrollable manner. As such, the substrates possessing eclipsing carboxylate and sulfinate esters accepted two organic ligands at the carboxylate functionality and one at the sulfinyl group. When isomer mixtures of sterically encumbered sulfinate esters were reacted, a single sulfoxide stereochemistry resulted. A mechanism involving the intermediacy of a sulfurane is proposed to account for the experimental observations.