Abstract
New reactivity patterns: Gold(I) catalyzes the conversion of cyclopentenes (1/1′) into cyclohexadienes (2/3). This profound skeleton rearrangement comprises ring expansion and a [1,2]-alkynyl shift, and is thought to be initiated by the cleavage of the bridging CC bond. The proposed allyl–gold cation intermediate is trapped with alcohols to provide bicyclo[3.2.1]octadiene and tricyclo[3.2.1.02,7]octane derivatives.
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