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

Łukasz Albrecht; Dariusz Deredas; Jakub Wojciechowski; Wojciech M. Wolf; Henryk Krawczyk

doi:10.1055/s-0031-1289629

PAPER

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

Łukasz Albrecht^a, Dariusz Deredas^a, Jakub Wojciechowski^b, Wojciech M. Wolf^b, 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

Abstract

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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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References

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