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Alcohols, ethers, carbohydrates, and related compounds. II. The anomeric effect
Author(s) -
Lii JennHuei,
Chen KuoHsiang,
Durkin Kathleen A.,
Allinger Norman L.
Publication year - 2003
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10269
Subject(s) - anomeric effect , chemistry , anomer , torsion (gastropod) , force field (fiction) , ab initio , computational chemistry , ab initio quantum chemistry methods , standard enthalpy of formation , stereochemistry , molecule , organic chemistry , physics , medicine , surgery , quantum mechanics
The anomeric effect has been studied for a variety of compounds using the MM4 force field, and also using MP2/6‐311++G(2d,2p) ab initio calculations and experimental data for reference purposes. Geometries and energies, including conformational, rotational barriers, and heats of formation were examined. Overall, the agreement of MM4 with the experimental and ab initio data is good, and significantly better than the agreement obtained with the MM3 force field. The anomeric effect is represented in MM4 by various explicit terms in the force constant matrix. The bond length changes are accounted for with torsion‐stretch elements. The angle changes are accounted for with torsion‐bend elements. The energies are taken into account with a number of torsional terms in the usual way. A torsion‐torsion interaction is also of some importance. With all of these elements included in the calculation, the MM4 results now appear to be adequately accurate. The heats of formation were examined for a total of 12 anomeric compounds, and the experimental values were fit by MM4 with an RMS error of 0.42 kcal/mol. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1473–1489, 2003