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Title: Hydride-mediated homogeneous catalysis. Catalytic reduction of. alpha. ,. beta. -unsaturated ketones using ((Ph sub 3 P)CuH) sub 6 and H sub 2

Abstract

Hydride-mediated reduction of {alpha},{beta}-unsaturated ketones catalytic in the hydride reagent is reported using ((Ph{sub 3}P)CuH){sub 6} and molecular hydrogen. The reaction proceeds at room temperature and is highly regioselective, affording either the product of conjugate reduction or complete 1,4- and 1,2-reduction to the saturated alcohol, depending on reaction conditions. In the presence of excess phosphine, the process is homogeneous and chemoselective: isolated double bonds are not hydrogenated, even under forcing conditions. This novel catalytic reduction appears to proceed via the heterolytic activation of molecular hydrogen by highly reactive copper(I) enolate and alkoxide intermediates.

Authors:
;  [1]
  1. Indiana Univ., Bloomington (USA)
Publication Date:
OSTI Identifier:
7157203
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (USA)
Additional Journal Information:
Journal Volume: 111:24; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 08 HYDROGEN; KETONES; REDUCTION; CATALYSIS; DATA ANALYSIS; EXPERIMENTAL DATA; HYDROGEN; HYDROGENATION; MEASURING INSTRUMENTS; MEASURING METHODS; CHEMICAL REACTIONS; DATA; ELEMENTS; INFORMATION; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; 400000* - Chemistry; 400201 - Chemical & Physicochemical Properties; 080800 - Hydrogen- Properties & Composition

Citation Formats

Mahoney, W S, and Stryker, J M. Hydride-mediated homogeneous catalysis. Catalytic reduction of. alpha. ,. beta. -unsaturated ketones using ((Ph sub 3 P)CuH) sub 6 and H sub 2. United States: N. p., 1989. Web. doi:10.1021/ja00206a008.
Mahoney, W S, & Stryker, J M. Hydride-mediated homogeneous catalysis. Catalytic reduction of. alpha. ,. beta. -unsaturated ketones using ((Ph sub 3 P)CuH) sub 6 and H sub 2. United States. https://doi.org/10.1021/ja00206a008
Mahoney, W S, and Stryker, J M. 1989. "Hydride-mediated homogeneous catalysis. Catalytic reduction of. alpha. ,. beta. -unsaturated ketones using ((Ph sub 3 P)CuH) sub 6 and H sub 2". United States. https://doi.org/10.1021/ja00206a008.
@article{osti_7157203,
title = {Hydride-mediated homogeneous catalysis. Catalytic reduction of. alpha. ,. beta. -unsaturated ketones using ((Ph sub 3 P)CuH) sub 6 and H sub 2},
author = {Mahoney, W S and Stryker, J M},
abstractNote = {Hydride-mediated reduction of {alpha},{beta}-unsaturated ketones catalytic in the hydride reagent is reported using ((Ph{sub 3}P)CuH){sub 6} and molecular hydrogen. The reaction proceeds at room temperature and is highly regioselective, affording either the product of conjugate reduction or complete 1,4- and 1,2-reduction to the saturated alcohol, depending on reaction conditions. In the presence of excess phosphine, the process is homogeneous and chemoselective: isolated double bonds are not hydrogenated, even under forcing conditions. This novel catalytic reduction appears to proceed via the heterolytic activation of molecular hydrogen by highly reactive copper(I) enolate and alkoxide intermediates.},
doi = {10.1021/ja00206a008},
url = {https://www.osti.gov/biblio/7157203}, journal = {Journal of the American Chemical Society; (USA)},
issn = {0002-7863},
number = ,
volume = 111:24,
place = {United States},
year = {Wed Nov 22 00:00:00 EST 1989},
month = {Wed Nov 22 00:00:00 EST 1989}
}