286472-39-7Relevant articles and documents
The Interaction of π orbitals with a carbocation over three σ bonds
Lambert, Joseph B.,Ciro, Sol M.
, p. 1940 - 1945 (1996)
The semi-π analogue of double hyperconjugation ("hyperconjugation/conjugation") has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate (5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by ks mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the γ,δ π orbitals with the α,β σ orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.
