On the Thermodynamic Control of Ring Opening of 4-Substituted 1,3,3-Tris-Carbethoxycyclobutene and the Role of the C-3 Substituent in Masking the Kinetic Torquoselectivity

The predominant transformations of 4-methyl- and 4-phenyl-1,3,3-tris-carbethoxycyclobutenes to s-trans-trans-1,1,3-tris-carbethoxy-4-methyl- and 4-phenyl-1,3-butadienes, respectively, proceed through a pathway entailing heterolytic cleavage of sC3C4 bond rather than the usual four-electron conrotatory ring opening. The adventitious or in situ generated halogen acid catalyzes the reaction by either protonation of one of the two ester groups on C3 and, thus, weakening sC3C4 bond to allow its heterolytic cleavage and formation of a stable cation or protonation followed by halide ion attack in SN2 manner on the methyl/phenyl-bearing carbon. Reorganization of the cation species formed in the former event and elimination of the elements of halogen acid from the halo-species formed in the latter event generate the observed product. The nucleophilic attack of DMSO to bring about heterolytic SN2 cleavage of sC3C4 bond is also discussed.