Synthesis of Cyclitols via Cyclopropanation/Palladium-Catalyzed Ring Opening

Abstract

The stereoselective syntheses of three cyclitols, 5a-carba-α-d-rhamnopyranose, 5a-carba-β-d-digitoxopyranose, and 5a-carba-α-l-rhamnopyranose, have been achieved. The routes rely upon a Simmons-Smith cyclopropanation and diastereospecific ring opening of cyclopropanol under Pd/C hydrogenation conditions to prepare the α-methyl ketone. A sequence of diastereoselective reduction, dihydroxylation, and/or Myers’ reductive 1,3-rearrangement were used to install the desired stereochemistry.

Key words

cyclitol - carbasugar - cyclopropanol - Pd/C hydrogenation - ring opening

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