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Using theozymes for designing transition‐state analogs for the intramolecular aldol reaction of δ‐diketones
Author(s) -
Arnó Manuel,
Domingo Luis R.
Publication year - 2001
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.1070
Subject(s) - aldol reaction , intramolecular force , chemistry , computational chemistry , transition state , aldol condensation , catalysis , stereoselectivity , base (topology) , stereochemistry , combinatorial chemistry , organic chemistry , mathematical analysis , mathematics
Abstract Two theozymes for the intramolecular aldol reaction of δ‐diketones have been studied using ab initio methods. The presence of both acid/base residues favors several steps of the aldol reaction. The appropriate positioning of these residues can accelerate one of two diastereromeric reaction pathways, the catalyzed aldol reaction being highly stereoselective. Analysis of the geometrical parameters, charge distribution, and the shape of molecular electrostatic potential for the corresponding acid/base catalyzed transition structure allows us to design adequate transition‐state analogs to favor a reactive channel of this intramolecular aldol reaction. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 83: 338–347, 2001