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Conformational effects on the mechanism of acid‐catalyzed dehydration of hexitols
Author(s) -
DošenMićović Lj.,
Čeković Ž.
Publication year - 1998
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/(sici)1099-1395(199812)11:12<887::aid-poc78>3.0.co;2-9
Subject(s) - chemistry , sn2 reaction , d mannitol , catalysis , dehydration , mechanism (biology) , reaction mechanism , polarity (international relations) , dehydration reaction , computational chemistry , stereochemistry , mannitol , organic chemistry , biochemistry , philosophy , epistemology , cell
Abstract The Monte Carlo search of the low‐energy regions of D ‐mannitol ( 4 ) and D ‐glucitol ( 5 ) conformational space was undertaken in order to investigate conformational effects on the stereochemistry of the acid‐catalyzed dehydrative cyclization reaction of 4 and 5 to the corresponding 1,4:3,6‐dianhydrohexitols. It was found that although dominant conformations in water resemble closely the crystal state conformations of 4 and 5, the same is not true in solvents of low polarity. The magnitudes of the calculated energies of the reactive conformations for the dehydrative cyclization reaction suggest an S N 2 mechanism with a late transition state. Copyright © 1998 John Wiley & Sons, Ltd.