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

J. Andrés; A. Arnau; E. Silla; J. Bertran; O. Tapia

doi:10.1016/0166-1280(83)80032-3

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

J. Andrés, A. Arnau, E. Silla, J. Bertran, O. Tapia

Department of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

11 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	49-54
Journal	Journal of Molecular Structure: THEOCHEM
Volume	105
Issue number	1-2
DOIs	https://doi.org/10.1016/0166-1280(83)80032-3
Publication status	Published - 1 Jan 1983

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

abstract = "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. {\textcopyright} 1983.",

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A theoretical study of the intramolecular solvolytic mechanism of the Meyer-Schuster reaction. MINDO/3 and CNDO/2 calculations of minimum energy paths. / Andrés, J.; Arnau, A.; Silla, E.; Bertran, J.; Tapia, O.

In: Journal of Molecular Structure: THEOCHEM, Vol. 105, No. 1-2, 01.01.1983, p. 49-54.

Research output: Contribution to journal › Article › Research › peer-review

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T1 - A theoretical study of the intramolecular solvolytic mechanism of the Meyer-Schuster reaction. MINDO/3 and CNDO/2 calculations of minimum energy paths

AU - Andrés, J.

AU - Arnau, A.

AU - Silla, E.

AU - Bertran, J.

AU - Tapia, O.

PY - 1983/1/1

Y1 - 1983/1/1

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AB - 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.

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DO - 10.1016/0166-1280(83)80032-3

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