Nickel-Catalyzed Conjugate Addition of Alkynyl Groups to. α,β-Unsaturated Ketones

Jeffrey Schwartz; Denise B. Carr; Robert T. Hansen; Fabian M. Dayrit

doi:10.1021/jo01303a024

Nickel-Catalyzed Conjugate Addition of Alkynyl Groups to. α,β-Unsaturated Ketones

Jeffrey Schwartz, Denise B. Carr, Robert T. Hansen, Fabian M. Dayrit

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99 Scopus citations

Abstract

The complex formed by reaction of Ni(acac)2 and DiBAH (1:1) catalyzes conjugate addition of dialkylaluminum acetylides to, ß enones; on hydrolysis, 3-alkynyl ketones are produced in high yield. Through this procedure conjugate addition of alkynyl groups to either S-cis or S-trans enones can be effected. This procedure is the first one which permits conjugate addition of terminal alkynyl units to ordinary S-trans enones. In cases where more than one stereochemical outcome is possible, conjugate addition of alkynyl units gives only one of these. Only 1,4-addition is observed and this only of the alkynyl unit. Complications arising from oxygen substitution in the alkynyl side chain are described.

Original language	English (US)
Pages (from-to)	3053-3061
Number of pages	9
Journal	Journal of Organic Chemistry
Volume	45
Issue number	15
DOIs	https://doi.org/10.1021/jo01303a024
State	Published - Jul 1980

All Science Journal Classification (ASJC) codes

Organic Chemistry

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title = "Nickel-Catalyzed Conjugate Addition of Alkynyl Groups to. α,β-Unsaturated Ketones",

abstract = "The complex formed by reaction of Ni(acac)2 and DiBAH (1:1) catalyzes conjugate addition of dialkylaluminum acetylides to, {\ss} enones; on hydrolysis, 3-alkynyl ketones are produced in high yield. Through this procedure conjugate addition of alkynyl groups to either S-cis or S-trans enones can be effected. This procedure is the first one which permits conjugate addition of terminal alkynyl units to ordinary S-trans enones. In cases where more than one stereochemical outcome is possible, conjugate addition of alkynyl units gives only one of these. Only 1,4-addition is observed and this only of the alkynyl unit. Complications arising from oxygen substitution in the alkynyl side chain are described.",

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year = "1980",

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language = "English (US)",

volume = "45",

pages = "3053--3061",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Nickel-Catalyzed Conjugate Addition of Alkynyl Groups to. α,β-Unsaturated Ketones

AU - Schwartz, Jeffrey

AU - Carr, Denise B.

AU - Hansen, Robert T.

AU - Dayrit, Fabian M.

PY - 1980/7

Y1 - 1980/7

N2 - The complex formed by reaction of Ni(acac)2 and DiBAH (1:1) catalyzes conjugate addition of dialkylaluminum acetylides to, ß enones; on hydrolysis, 3-alkynyl ketones are produced in high yield. Through this procedure conjugate addition of alkynyl groups to either S-cis or S-trans enones can be effected. This procedure is the first one which permits conjugate addition of terminal alkynyl units to ordinary S-trans enones. In cases where more than one stereochemical outcome is possible, conjugate addition of alkynyl units gives only one of these. Only 1,4-addition is observed and this only of the alkynyl unit. Complications arising from oxygen substitution in the alkynyl side chain are described.

AB - The complex formed by reaction of Ni(acac)2 and DiBAH (1:1) catalyzes conjugate addition of dialkylaluminum acetylides to, ß enones; on hydrolysis, 3-alkynyl ketones are produced in high yield. Through this procedure conjugate addition of alkynyl groups to either S-cis or S-trans enones can be effected. This procedure is the first one which permits conjugate addition of terminal alkynyl units to ordinary S-trans enones. In cases where more than one stereochemical outcome is possible, conjugate addition of alkynyl units gives only one of these. Only 1,4-addition is observed and this only of the alkynyl unit. Complications arising from oxygen substitution in the alkynyl side chain are described.

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Nickel-Catalyzed Conjugate Addition of Alkynyl Groups to. α,β-Unsaturated Ketones

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