Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Theoretical Studies on the Gas-Phase Wolff Rearrangement of Ketocarbenes

  • Published : 1997.04.20
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Abstract

The substituent effects in the gas-phase rearrangement of carbenes to ketenes involved in the Wolff reaction have been investigated theoretically using the AM1 method. In the initial state, carbene, there is a relatively strong vicinal n-σ* interaction between the lone pair (n) and carbonyl group (σ*). In the bridged transition state (TS), electronic charge is transferred from the migrating ring (Z-ring) toward the nonmigrating ring (Y-ring). The carbenes are stabilized by an electron donor Y (δσY < 0) whereas the TS is stabilized by an electron acceptor Y (δσY > 0). Multiple regression analysis of log (kYZ/kHH)(=-δΔG≠/2.3RT) leads to a relatively large negative cross-interaction constant, ρYZ=-0.53, log (kYZ/kHH)=2.96 σY--1.40 σZ-0.53 σY-σZ reflecting an extensive structural change in the transition state due to the stabilization of the initial state by the vicinal n-σ* overlap. When the solvent (water) effects are accounted for by the SM2.1 model of the Cramer and Truhlar method, the magnitude of all the selectivity parameters, ρY-, ρZ and ρYZ (=-0.66) are increased.

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