A new umpolung for direct γ-regioselective nucleophilic addition of alcohols to γ-enolizable α, β-unsaturated aldehydes. Issue 25 (21st June 2017)

• Record Type: Journal Article
• Authors: Arimitsu, Satoru; Oshiro, Mari; Yonamine, Tsunaki
• Is Part Of: Tetrahedron letters. Volume 58:Issue 25(2017)
• Page Start: 2517
• Page End: 2520
• Publication Date: 2017-06-21
• Subjects: Umpolung -- γ-Enolizable α, β-unsaturated aldehydes -- Cross-dehydrogenative coupling -- Brønsted acids -- γ-Regioselective; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2017.05.058
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: A new umpolung of γ-enolizable α, β-unsaturated aldehydes was developed. The reactions showed excellent γ-regioselectivity and E -stereoselectivity. The addition of HFIP was found to accelerate the reaction. The reaction showed a wide range of substrates. Abstract: A direct γ-regioselective nucleophilic addition of alcohols toward γ-enolizable α, β-unsaturated aldehydes was developed using a catalytic amount of MeSO3 H (30 mol%) and a stoichiometric amount of chloranil (1.0 equiv) as the oxidant. The addition of hexafluoroisopropanol (HFIP) was found to accelerate this cross-dehydrogenative coupling, furnishing diverse alcoholic adducts with high γ-regio- and E -stereoselectivities.