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A theoretical study of hemiacetal formation from the reaction of methanol with derivatives of CX 3 CHO (X = H, F, Cl, Br and I)
Author(s) -
Azofra Luis Miguel,
Alkorta Ibon,
Elguero José
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3017
Subject(s) - hemiacetal , chemistry , methanol , molecule , stereocenter , chirality (physics) , catalysis , transition state , autocatalysis , stereochemistry , medicinal chemistry , computational chemistry , photochemistry , organic chemistry , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark , enantioselective synthesis
A theoretical study of the hemiacetal formation reaction between methanol and CX 3 CHO (X = H, F, Cl, Br, and I) has been carried out using density functional theory and Becke, three‐parameter, Lee–Yang–Parr/6‐311++G(d,p) computational methods. The stationary points of the reaction between the isolated molecules and the reaction catalyzed by an additional methanol molecule have been characterized. Because the final products present a stereogenic center, the potential autocatalysis of the reaction has been examined and also the possibility of spontaneous generation of chirality when the hemiacetal molecules are involved in the transition state structure. High barriers are found in the reaction between the isolated molecules that are reduced by the assistance of an additional molecule (methanol or hemiacetal product). The reactions catalyzed by the hemiacetal products show higher barriers than the one catalyzed by methanol. Copyright © 2012 John Wiley & Sons, Ltd.