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Synthesis 2012(2): 247-252  
DOI: 10.1055/s-0031-1289629
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantio- and Diastereoselective Synthesis of β,γ,γ,δ-Tetrasubstituted α-Methylene-δ-lactones

Łukasz Albrechta, Dariusz Deredasa, Jakub Wojciechowskib, Wojciech M. Wolfb, Henryk Krawczyk*a
a Institute of Organic Chemistry, Technical University (Politechnika), Żeromskiego 116, 90-924 Łódź, Poland
Fax: +48(42)63655 30; e-Mail: henkrawc@p.lodz.pl;
b Institute of General and Ecological Chemistry, Technical University (Politechnika), Żeromskiego 116, 90-924 Łódź, Poland
Further Information

Publication History

Received 5 September 2011
Publication Date:
01 December 2011 (online)

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Abstract

The synthesis of two α-(diethoxyphosphoryl)-α,β-unsaturated δ-lactones with 98% ee has been developed using (S)-3-aryl-3-hydroxy-2,2-dimethylpropanals, easily accessible via direct, asymmetric organocatalytic aldol reaction, as the starting materials. The lactones were transformed into the corresponding α-methylene-δ-lactones in a two-step process involving Michael addition followed by Horner-Wadsworth-Emmons olefination without loss of enantiomeric purity. Furthermore, it was shown that diastereoselectivity of the Michael addition can be fully controlled by the C6 stereogenic center in the intermediate lactones. A transition-state model rationalizing the stereochemical outcome of the reaction was proposed.

Key words

Knoevenagel condensation - Michael addition - HWE olefination - β-hydroxyaldehydes - α-methylene-δ-lactones

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Crystallographic data (excluding structure factors) for the structure reported herein have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication CCDC 822405. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Any request should be accompanied by a full literature citation.