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Synthesis 2008(19): 3142-3147  
DOI: 10.1055/s-2008-1067260
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Enantio- and Diastereodivergent Synthetic Route to Multifarious Cyclitols from d-Xylose via Ring-Closing Metathesis

Giovanni Luchettia, Kejia Dingb, Marc d’Alarcao*b, Alexander Kornienko*a
a Department of Chemistry, New Mexico Institute of Mining and Technology, Socorro, NM 87801, USA
Fax: +1(575)8355364; e-Mail: akornien@nmt.edu;
b Department of Chemistry, San José State University, One Washington Square, San José, CA 95192-0101, USA
Fax: +1(408)9244945; e-Mail: mdalarcao@science.sjsu.edu;
Further Information

Publication History

Received 20 May 2008
Publication Date:
05 September 2008 (online)

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Abstract

Short stereoselective syntheses of various cyclitols, including the derivatives of conduritol B, conduritol F, myo-inositol, and chiro-inositol have been accomplished. The key steps in the syntheses are a ring-closing metathesis process and a diastereodivergent organometallic addition to a d-xylose-derived aldehyde.

Key words

conduritol - inositol - Grignard - stereochemistry model - chelation - Felkin-Anh - cyclophellitol - latent symmetry

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16

After our original disclosure of these results (ref. 14), Madsen and co-workers reported that performing this reaction with vinylmagnesium chloride in toluene leads to a higher (5:1) syn selectivity (ref. 15b).

21

Both the organometallic reagent and the reaction solvent are important since Lewis basic solvents such as THF or Et2O can diminish chelation by strongly coordinating to the metal species.