Regiochemistry in radical cyclization of allenes

The cyclization of allenic radicals was systematically studied for the first time by computational methods. It was found that the theoretical results at the ONIOM(QCISD(T)/6-311+G(2df,2p):UB3LYP/6-311+G(2df,2p)) level were in good agreement with all the available experimental data. For the cyclization of penta-3,4-dien-1-yl radicals the major product was penta-1,2-diene from direct reduction whereas a small amount of vinylcyclopropane may also be produced. For the cyclization of hexa-4,5-dien-1-yl radicals the major product is 1-methyl-cyclopentene. Furthermore, for the cyclization of hepta-5,6-dien-1-yl radicals both vinylcyclopentane and 1-methyl-cyclohexene are produced. Marcus theory analysis indicated that the formation of an olefinic radical product always had a lower intrinsic energy barrier than the formation of an allylic radical product. On the other hand, the formation of an olefinic radical product was always much less favorable than the formation of an allylic radical product in the thermodynamic term. For the cyclization of substituted hexa-4,5-dien-1-yl radicals, substitution at the allene moiety does not affect the regioselectivity where the allylic radical product is always favored. For the cyclization of hepta-5,6-dien-1-yl radicals, substitution at the allene moiety dramatically affects the regioselectivity, where some radical-stabilizing groups such as -CN and -COMe may even completely reserve the regioselectivity.

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