Using density functional theory to calculate the anomeric effect in hydroxylamine and hydrazide derivatives of tetrahydropyran |
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| Authors: | Joseph M Langenhan Ryan P McLaughlin Steven A Loskot Leonardo M Rozal Mackenzie S Clay Peter J Alaimo |
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| Institution: | 1. Department of Chemistry, Seattle University, Seattle, WA, USAlangenha@seattleu.edu;3. Department of Chemistry, Seattle University, Seattle, WA, USA |
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| Abstract: | Little is known about the magnitude of the anomeric effect in N-glycosylated oxyamines and hydrazides, limiting efforts toward the design of chemoselective acceptors that impose a stereochemical preference on glycosylation reactions. Thus, density functional theory (DFT) calculations were conducted to estimate the magnitude of the anomeric effect in N,O-dimethyl-N-(tetrahydro-2H-pyran-2-yl)hydroxylamine (1) and N'-(tetrahydro-2H-pyran-2-yl)acetohydrazide (3). The results show that N,O-dimethyl-N-(tetrahydro-2H-pyran-2-yl)hydroxylamine (1) displays a significant anomeric effect (AEcorr = 1.38 kcal/mol) and that N'-(tetrahydro-2H-pyran-2-yl)acetohydrazide (3) displays a modest anomeric effect (AEcorr = 0.54 kcal/mol). |
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| Keywords: | Anomeric effect chemoselective glycosylation conformational analysis DFT calculations |
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