Abstract
Ab initio procedures were used to characterize the transition states for α-cleavage and subsequent H-transfer starting with ionized cyclopentanone (1). The objective was to determine whether the parts of the ion disconnected by the bond cleavage remain in close association through the H-transfer. The transition state for C-C bond cleavage is close in energy to the resulting distonic ion, which is a stable species, and far in geometry from any transition state involving H-transfer. We find no evidence for any concertedness or “quasiconcertedness” in this reaction. Ring-opening H-transfer in 1 and ion-neutral complex-mediated alkane eliminations are compared.
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Hudson, C.E., McAdoo, D.J. Ab initio characterization of ring-opening H-transfer in ionized cyclopentanone: Similarity to ion-neutral complex-mediated alkane eliminations. J Am Soc Mass Spectrom 7, 1251–1254 (1996). https://doi.org/10.1016/S1044-0305(96)00103-1
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DOI: https://doi.org/10.1016/S1044-0305(96)00103-1