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Synthesis 2013; 45(10): 1319-1324
DOI: 10.1055/s-0032-1318507
DOI: 10.1055/s-0032-1318507
paper
Novel Synthesis of Butyl (S)-2-Hydroxybutanoate, the Key Intermediate of PPARα Agonist (R)-K-13675 from Butyl (2S,3R)-Epoxybutanoate and Butyl (S)-2,3-Epoxypropanoate
Further Information
Publication History
Received: 08 February 2013
Accepted after revision: 06 March 2013
Publication Date:
03 April 2013 (online)
Abstract
Novel synthetic methods for the production of butyl (S)-2-hydroxybutanoate starting from butyl (2S,3R)-epoxybutanoate or butyl (S)-2,3-epoxypropanoate were established. The former method utilized the regioselective thiolysis of the epoxybutanoate mediated by scandium triflate and subsequent reductive cleavage of the thioether to give butyl (S)-2-hydroxybutanoate with stereochemical retention in quantitative yield. The latter method utilized one-step conversion by a combination of methylmagnesium bromide and copper catalyst in high yield.
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This mechanism presumably involves anchimeric assistance of the carboxy group in the decomposition of an intermediate diazonium ion, leading to an α-hydroxy acid with retention of configuration. See the following reference:
The reaction of butyl (S)-2-bromobutanoate obtained via diazotization of (S)-2-aminobutanoic acid with phenol accompanied with racemization (~81% ee):
Refer to the following articles:
Refer to the following articles: