Asymmetric Synthesis of (S,S)- and (R,R)-2-Methylthreitol

Abstract

The asymmetric synthesis of (S,S)- and (R,R)-2-methylthreitol was carried out, starting from the SAMP or RAMP hydrazone of 2,2-dimethyl-1,3-dioxan-5-one. The protocol involves an enantioselective α-alkylation as a key step. The second stereogenic center was installed by either nucleophilic 1,2-addition or diastereo­selective epoxidation with bis(acetylacetonato)oxovanadium(IV) [VO(acac)₂] as catalyst. The title compounds were obtained in excellent diastereo- and enantiomeric excesses (≥98% de, 98% ee) and in good overall yields (40-61%).

Key words

asymmetric synthesis - epoxidation - tetrols - α-alkylation - SAMP/RAMP hydrazones - 1,2-addition

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Moen, A. R.; Ruud, K.; Anthonsen, T. Eur. J. Org. Chem., 2007, 1262.

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Crystallographic data have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 634702. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone],
e-mail: [e-mail], or www.ccdc.cam.ac.uk].