Kinetic evidence for remote pi-aryl participation in the BF3-catalyzed rearrangement of [2 + 2] photocycloadducts of diarylhomobenzoquinones with diphenylacetylene

reaction: see text] The BF(3)-catalyzed rearrangement of cyclobutene-fused m- and p-substituted diarylhomobenzoquinones exclusively gave the keto-alcohols via a Wagner-Meerwein vinyl-anion migration followed by the annulation of a delta-located endo-aryl group. The Hammett treatments for the endo/exo substituent effects, as well as the kinetic solvent effects, indicated that this reaction proceeds through the concerted S(N)2-like mechanism involving a rate-determining endo-aryl-assisted transition state.