ISSN:
0947-6539
Keywords:
ab initio calculations
;
Henry reaction
;
nitroaldol reactions
;
reaction mechanisms
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030105
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