Controlling benzylic and anomeric functionality and stereochemistry: methodolgy and syntheses utilising intramolecular ionic hydrogenation

McCombie, Stuart W, Ortiz, Claudio, Cox, Brian and Ganguly, Ashit K (1993) Controlling benzylic and anomeric functionality and stereochemistry: methodolgy and syntheses utilising intramolecular ionic hydrogenation. Synlett, 1993 (8). pp. 541-547. ISSN 0936-5214

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Abstract

Intramolecular hydride transfer from a hydroxyl-tethered SiH unit to a stabilised carbonium ion is shown to be a useful method for stereochemical control in benzylic and carbohydrate systems, as exemplified by racemic and nonracemic syntheses of key intermediates for the pseudopterosin/secopseudopterosin family, and by the synthesis of 2-deoxy-C-glycosides. These syntheses illustrate and compare two alternative methods of carbonium ion generation: olefin protonation, and Lewis acid-promoted sulfone ionisation. Simple model systems are used to show that ring size restrictions to hydride transfer in a 5-membered ring may be overcome by the appropriate choice of reagent, permitting the reaction to be used for stereochemical control from a vicinal, hydroxyl-bearing carbon.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry
Depositing User: Tom Gittoes
Date Deposited: 14 Jan 2015 09:42
Last Modified: 14 Jan 2015 09:42
URI: http://sro.sussex.ac.uk/id/eprint/52121
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