Journal of Organic Chemistry 2014-06-06

Synthesis of allo- and epi-inositol via the NHC-catalyzed carbocyclization of carbohydrate-derived dialdehydes.

Kieran P Stockton, Ben W Greatrex, Dennis K Taylor

Index: J. Org. Chem. 79(11) , 5088-96, (2014)

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Abstract

A synthesis of carbocyclic sugars from carbohydrate-derived dialdehydes using organocatalysis has been developed. Sorbitol, mannitol, and galactitol were converted via 1,6-tritylation, perbenzylation or permethylation, detritylation, and Swern oxidation into 2,3,4,5-tetra-O-alkyl-dialdoses that were cyclized via the benzoin reaction promoted by a triazolium carbene. Manno- and galacto-configured dialdehydes gave predominantly single inosose stereoisomers in up to 75% yield if the mixture was acetylated prior to isolation while the gluco-dialdehyde afforded a mixture of three stereoisomers in 61% overall yield. The inososes were stereospecifically reduced using sodium borohydride and then deprotected to give allo- and epi-inositol in good yield that confirmed the structural and stereochemical assignments.