Metal-free reductive cleavage of c-o sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor

S.P.Y. Cutulic, N.J. Findlay, S.Z. Zhou, E.J.T. Chrystal, J.A. Murphy

Research output: Contribution to journalArticle

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Abstract

Neutral organic electron-donor 7, formally a pyridinylidene carbene dimer, effects reductive cleavage of C-O sigma-bonds in acyloin derivatives Ar(CO)CRR'OX (X = OAc, OPiv, OBz, OMs) and this represents the first cleavage of C-O sigma-bonds by a neutral organic electron-donor. The methodology is applicable to a large array of substrates and the reduced counterparts were isolated in good to excellent yields. For certain substrates, donor 7 behaves as a base, effecting condensation reactions with some acetate ester derivatives of acyloins, leading to butenolides. The variation in reactivity among the different substrates was rationalized.
LanguageEnglish
Pages8713-8718
Number of pages5
JournalJournal of Organic Chemistry
Volume74
Issue number22
Publication statusPublished - 20 Nov 2009

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Metals
Derivatives
Electrons
Substrates
Condensation reactions
Carbon Monoxide
Dimers
Esters
Acetates
acyloin
carbene

Cite this

Cutulic, S.P.Y. ; Findlay, N.J. ; Zhou, S.Z. ; Chrystal, E.J.T. ; Murphy, J.A. / Metal-free reductive cleavage of c-o sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor. In: Journal of Organic Chemistry. 2009 ; Vol. 74, No. 22. pp. 8713-8718.
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Metal-free reductive cleavage of c-o sigma-bonds in acyloin derivatives by an organic neutral super-electron-donor. / Cutulic, S.P.Y.; Findlay, N.J.; Zhou, S.Z.; Chrystal, E.J.T.; Murphy, J.A.

In: Journal of Organic Chemistry, Vol. 74, No. 22, 20.11.2009, p. 8713-8718.

Research output: Contribution to journalArticle

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AU - Cutulic, S.P.Y.

AU - Findlay, N.J.

AU - Zhou, S.Z.

AU - Chrystal, E.J.T.

AU - Murphy, J.A.

PY - 2009/11/20

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AB - Neutral organic electron-donor 7, formally a pyridinylidene carbene dimer, effects reductive cleavage of C-O sigma-bonds in acyloin derivatives Ar(CO)CRR'OX (X = OAc, OPiv, OBz, OMs) and this represents the first cleavage of C-O sigma-bonds by a neutral organic electron-donor. The methodology is applicable to a large array of substrates and the reduced counterparts were isolated in good to excellent yields. For certain substrates, donor 7 behaves as a base, effecting condensation reactions with some acetate ester derivatives of acyloins, leading to butenolides. The variation in reactivity among the different substrates was rationalized.

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