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Ab Initio Models for the Nitroaldol (Henry) Reaction
Author(s) -
Lecea Begoña,
Arrieta Ana,
Morao Iñaki,
Cossío Fernando P.
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030105
Subject(s) - nitronate , nitroaldol reaction , ab initio , chemistry , stereoselectivity , nitro , nitromethane , transition state , computational chemistry , aldol reaction , organic chemistry , catalysis , enantioselective synthesis , alkyl
Ab initio calculations (up to MP4SDQ/6‐31+G * //MP2(FU)/6‐31+G * + δZPVE) on several model nitroaldol (Henry) reactions have been performed. It is found that the free nitronate anions react with aldehydes via transition states in which the nitro and carbonyl dipoles are antiperiplanar to each other. This kind of reaction yields anti (erythro) nitroalcohols as major products. The Henry reaction between lithium nitronates and aldehydes is predicted to occur via cyclic transition structures yielding syn nitroalcohols as major products. The stereocontrol in these model reactions is low. The factors affecting the stereoselectivity in the reaction between dilithiated nitronates and aldehydes are also discussed.