Kinetic Resolution of the Racemic 2-Hydroxyalkanoates Using the Enantioselective Mixed-Anhydride Method with Pivalic Anhydride and a Chiral Acyl-Transfer Catalyst

Autor:	Isamu Shiina, Keisuke Ono, Masuhiro Sugimoto, Akihiro Sekiguchi, Kenya Nakata
Rok vydání:	2010
Předmět:	Molecular Structure Chemistry Organic Chemistry Enantioselective synthesis Stereoisomerism General Chemistry Catalysis Chiral resolution Anhydrides Kinetic resolution Kinetics Transacylation Alkanes Organic chemistry Racemic mixture Moiety Pentanoic Acids Chirality (chemistry)
Zdroj:	Chemistry - A European Journal. 16:167-172
ISSN:	1521-3765 0947-6539
DOI:	10.1002/chem.200902257
Popis:	A variety of optically active 2-hydroxyalkanoates and the corresponding 2-acyloxyalkanoates are produced by the kinetic resolution of racemic 2-hydroxyalkanoates by using achiral 2,2-diarylacetic acid with hindered carboxylic anhydrides as the coupling reagents. The combined use of diphenylacetic acid, pivalic anhydride, and (+)-(R)-benzotetramisole ((R)-BTM) effectively produces (S)-2-hydroxyalkanoates and (R)-2-acyloxyalkanoates from the racemic 2-hydroxyalkanoates (s-values=47-202). This protocol directly provides the desired chiral 2-hydroxyalkanoate derivatives from achiral diarylacetic acid and racemic secondary alcohols that do not include the sec-phenethyl alcohol moiety by using the transacylation process to generate the mixed anhydrides from the acid components with bulky carboxylic anhydrides under the influence of the chiral acyl-transfer catalyst. The transition state that provides the desired (R)-2-acyloxyalkanoate from (R)-2-hydroxyalkanoate included in the racemic mixture is disclosed by DFT calculations, and the structural features of the transition form are also discussed.
Databáze:	OpenAIRE
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