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Gas-phase Carbanion Rearrangements. Deprotonated Benzyl and Allyl Ethers

DOI: 10.1039/P29880000497

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 497 - 506 (1988)

Update date:2022-08-05

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Authors:

Eichinger, Peter C. H.Eichinger, Peter C. H.

Bowie, John H.Bowie, John H.

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Article abstract of DOI:10.1039/P29880000497

The following systems have been studied: (i) the ion PhOC(1-)Ph2 on collisional activation undergoes Wittig rearrangement to Ph3CO(1-) before fragmentation; (ii) PhOC(1-)HCH=CH2 undergoes competing rearrangements, viz.Wittig rearrangement to Ph(CH2=CH)CHO(1-) and anionic Claisen rearrangement to (HO) deprotonated o-allylphenol, with the former reaction predominating; (iii) deprotonation of dibenzyl ether yields an unstable species wich forms PhCH2 (1-): no Wittig rearrangement is observed in the gas phase although it occurs in the condensed phase; and (iv) PhCH2OCH2CH=CH2 deprotonates to form the two interconvertible anions PhC(1-)HOCH2CH=CH2 and PhCH2OC(1-)HCH=CH2 of which the former is the more stable.Both ions give minor Wittig products, but the major process is loss of H2O to form a deprotonated dihydronaphthalene.There is some analogy between gas-phase and condensed-phase reactions in this system.The condensed-phase reaction of allyl benzyl ether under forcing conditions (lithium di-isopropylamide/tetrahydrofuran-hexamethylphosphoramide) gives the products 1-phenyl-but-3-en-1-ol, 1,2-dihydronaphthalene, and 1-(o-tolyl)prop-2-en-1-ol in the approximate ratio 4:3:1.

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