129247-70-7Relevant academic research and scientific papers
Generation of α-D-Glucopyranosylacetonitrilium Ions. Concerning the Reverse Anomeric Effect
Ratcliffe, Andrew J.,Fraser-Reid, Bert
, p. 747 - 750 (2007/10/02)
Reaction of the α- and β-anomers of the pent-4-enyl D-glucopyranoside (10) with N-bromosuccinimide in dry acetonitrile generated stereospecifically the α-D-glucopyranosylacetonitrilium ion (5α), which reacts in situ with 2-chlorobenzoic acid to afford the α-imide (8α).The result is in contrast to that predicted by the reverse anomeric effect and previous work on trapping carbohydrate acetonitrilium ions with 2-chlorobenzoic acid.The unusually large J12 7.3 Hz for 1-H of (8α) is rationalised by a substantial flattening of the pyranose ring at C-1 and C-2.Molecular dynamic studies on the model α-imide (12) support a flattened 4C1 conformation.Treatment of imide (8α) with sodium methoxide leads to the α-2-chlorobenzamide (9α), which was substantiated by intependent synthesis of the β-2-chlorobenzamide (9β).
