Mild Synthesis of Protected α-D-Glycosyl Iodides

Does Neighboring Group Participation by Non-Vicinal Esters Play a Role in Glycosylation Reactions? Effective Probes for the Detection of Bridging Intermediates

“…The isolation of the hydrolysis product 18 on activation with NIS/Tf 2 O presumably is due to trapping of a cyclic intermediate 19 , before loss of the tert -butyl group, by iodide or by succinimide ( vide infra ) to give an unstable orthocarbonate-type species 20 which undergoes hydrolysis on work up (Scheme 4). We prefer this mechanism over the trapping of the glycosyl oxocarbenium ion by iodide or succinimide, followed by hydrolysis on work up, as both glycosyl iodides 35 and succinimides 36 have been demonstrated on numerous occasions to be isolable substances that are readily handled under standard conditions.…”

Stereoselective Chemical 1,2-cis O-Glycosylation: From ‘Sugar Ray’ to Modern Techniques of the 21st Century

“…44 Glycosyl iodides generated in situ from glycosyl bromides or chlorides with NaI were first applied to the synthesis of simple glycosides. [80][81][82] These derivatives have a limited shelf-life and therefore, are best used in situ; in most cases glycosyl iodides afforded the desired products with high stereoselectivity and yields. However, this method has not found a broad preparative application until recently when reliable methods for the generation of the glycosyl iodides have emerged.…”

Selective activation of glycosyl donors utilising electrochemical techniques: a study of the thermodynamic oxidation potentials of a range of chalcoglycosides

“…The solution was stirred for 15 min, at which point 2,3,4,6,-tetra-O-benzoyl--D-glucopyranosyl iodide30 (2.5 g, 3.54 mmol) was added and the reaction left to stir. The solution was stirred for 15 min, at which point 2,3,4,6,-tetra-O-benzoyl--D-glucopyranosyl iodide30 (2.5 g, 3.54 mmol) was added and the reaction left to stir.…”