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Synthesis 2008(19): 3171-3179  
DOI: 10.1055/s-2008-1067262
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Cyclitols via Cyclopropanation/Palladium-Catalyzed Ring Opening

Mingde Shan, George A. O’Doherty*
Department of Chemistry, West Virginia University, Morgantown, WV 26506, USA
Fax: +1(304)2934904; e-Mail: George.ODoherty@mail.wvu.edu;
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Publication History

Received 28 May 2008
Publication Date:
05 September 2008 (online)

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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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