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Synthesis 2012; 44(23): 3639-3648
DOI: 10.1055/s-0032-1316805
paper
© Georg Thieme Verlag Stuttgart · New York

Stereo- and Regioselective Synthesis of 2-Amino-3,5-diols via Stereospecific Crotyl Transfer and Regioselective Aminohydroxylation

Frank E. McDonald*
Department of Chemistry, Emory University, Atlanta, GA 30322, USA    Fax: +1(404)7276586   Email: fmcdona@emory.edu
,
Claney L. Pereira
Department of Chemistry, Emory University, Atlanta, GA 30322, USA    Fax: +1(404)7276586   Email: fmcdona@emory.edu
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Further Information

Publication History

Received: 06 August 2012

Accepted after revision: 26 September 2012

Publication Date:
24 October 2012 (online)

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Abstract

A short synthesis of 2-amino-3,5-diols is described, including the all-S isomer enigmol, a synthetic anticancer compound inspired by the structure of fumonisin B1. The synthetic route features 1) stereospecific crotyl transfer to tetradecanal via pericyclic oxonia-Cope rearrangement; 2) stereoselective epoxidation of the alkene; 3) regioselective epoxide opening with azide; and 4) reduction of azide to amine. This manuscript also corrects a structure assignment error in a previously reported synthesis of one of the diastereomers of enigmol.

Key words

allylation - rearrangement - regioselectivity - sphingolipids - stereoselective synthesis
 

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