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Controlling benzylic and anomeric functionality and stereochemistry: methodolgy and syntheses utilising intramolecular ionic hydrogenation
journal contributionposted on 2023-06-08, 19:32 authored by Stuart W McCombie, Claudio Ortiz, Brian Cox, Ashit K Ganguly
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.
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