NADH models: II. Mechanism of reduction of electrophilic olefins with 3,5-diethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine (1)

doi:10.1016/0045-2068(73)90030-8

Bioorganic Chemistry

Volume 2, Issue 4, September 1973, Pages 293-300

https://doi.org/10.1016/0045-2068(73)90030-8 Get rights and content

Abstract

Reduction of unsaturated acyl chlorides (5a-c) and acyl anhydrides (9a, b) by Hantzsch ester 3a proceeds by direct transfer of a hydrogen species (presumably a hydride ion). Critically designed experiments rule out a mechanism involving an acyl intermediate of type 2. The implications of these results in the mechanism of NADH-mediated reductions are discussed.

References (16)

E.M. Kosower
Biochim. Biophys. Acta
(1962)
U.K. Pandit et al.
Chem. Commun.
(1971)
T.C. Bruice et al.
E.M. Kosower
M.F Dunn
J.J. Steffens et al.
J. Amer. Chem. Soc.
(1971)
R.B. Woodward et al.

There are more references available in the full text version of this article.

Cited by (11)

Nadh models-19
1984, Tetrahedron
N-(Cyclopropylmethylene)phenylamines (1a-c), cyclopropyl 2-pyridyl ketones (5-c) and ethyl cyclopropylmethlenepyruvate (14) have been subjected to reduction by l,4-dihydropyridines [3,5-diethoxycarbonyl-2,6-dimethyl-l,4-dihydropyridine (2) and/or 1-benzyl-1,4-dihydronicotinamide (7)]in the presence of magnesium ions, and by tin hydrides. The reactions with 1,4-dihydropyridines do not involve cleavage of the three-membered ring in the reduction step. The observed acyclic product from 2-pyridyl 2,2-dimethylcyclopropyl ketone (5b) is a consequence of ring cleavage prior to reduction of the carbonyl function. In contrast, reduction of 1a-c and 5-c by tin hydrides leads to products in which the cylopropane moiety has undergone ring-opening. These findings support a hydride transfer mechanism for reductions with NADH models.
Reaction of N-benzyl-1,4-dihydronicotinamide with pyridine-2-carboxaldehyde. Formation of a new adduct
1976, Tetrahedron Letters
Readily available hydrogen bond catalysts for the asymmetric transfer hydrogenation of nitroolefins
2011, Organic and Biomolecular Chemistry
Asymmetric organocatalytic reductions mediated by dihydropyridines
2007, Organic and Biomolecular Chemistry
2-Phenylbenzimidazoline As A Reducing Agent In The Preparation Of Malononitriles From α,β-Unsaturated Dinitriles
1983, Synthetic Communications
Development in Dihydropyridine Chemistry
1982, Industrial and Engineering Chemistry Product Research and Development

View all citing articles on Scopus

View full text

NADH models: II. Mechanism of reduction of electrophilic olefins with 3,5-diethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine (1)

Abstract

Biochim. Biophys. Acta

Chem. Commun.

J. Amer. Chem. Soc.