Using density functional theory to calculate the anomeric effect in hydroxylamine and hydrazide derivatives of tetrahydropyran

作者：Langenhan Joseph M^*; McLaughlin Ryan P; Loskot Steven A; Rozal Leonardo M; Clay Mackenzie S; Alaimo Peter J

来源：Journal of Carbohydrate Chemistry, 2016, 35(2): 106-117.

DOI：10.1080/07328303.2016.1139122

• DFT calculations
• chemoselective glycosylation
• Anomeric effect
• conformational analysis

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 (AE(corr) = 1.38kcal/mol) and that N'-(tetrahydro-2H-pyran-2-yl)acetohydrazide (3) displays a modest anomeric effect (AE(corr) = 0.54kcal/mol).

• 出版日期2016-2-12