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The Mechanism of the Wolff‐Kishner Reduction, Elimination, and Isomerization Reactions
Author(s) -
Szmant H. H.
Publication year - 1968
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.196801201
Subject(s) - chemistry , isomerization , carbanion , solvent , reaction mechanism , concerted reaction , proton , mechanism (biology) , computational chemistry , organic chemistry , catalysis , physics , quantum mechanics , philosophy , epistemology
The mechanism of the Wolff‐Kishner reaction is discussed in the light of accumulated information about the kinetics, thermodynamics, and solvent effects of the process. Wolff‐Kishner reduction under normal conditions is thought to involve the trans hydrazone anion, which, in the rate‐determining step, exhibits a more or less concerted proton capture at the carbanion terminal and undergoes a solvent‐induced proton loss at the nitrogen terminal. The stereochemistry of the Wolff‐Kishner reduction is believed to be affected by the presence of “ortho” substituents and by a change to a nonpolar, aprotic reaction medium. The mechanism elaborated for the Wolff‐Kishner reduction is extended to the Wolff‐Kishner elimination and isomerization reactions. Conformational analysis of the intermediates permits correlation of the competitive reduction and elimination processes with the structures of acyclic systems.