A theoretical study of the intramolecular solvolytic mechanism of the Meyer-Schuster reaction. MINDO/3 and CNDO/2 calculations of minimum energy paths

Theoretical results give strong support to an intramolecular solvolytic mechanism for the Meyer-Schuster rearrangement. Both CNDO/2 and MINDO/3 reaction paths suggest that the possibility of a 1,3 propargylic shift across the triple bond in a model α-acetylenic tertiary alcohol can be discarded. The electronic structure of the reaction intermediate corresponds to an alkynyl cation interacting electrostatically with a water molecule. For non-aqueous solvents this result agrees with the formation of a stable alkynyl carbocation, which has been found experimentally. For aqueous solvents the nature of the reaction path leads to the conclusion that the intermolecular mechanism which has been proposed for this reaction is more realistic. © 1983.