A new umpolung for direct gamma-regioselective nucleophilic addition of alcohols to gamma-enolizable alpha,beta-unsaturated aldehydes

作者：Arimitsu Satoru^*; Oshiro Mari; Yonamine Tsunaki

来源：Tetrahedron Letters, 2017, 58(25): 2517-2520.

DOI：10.1016/j.tetlet.2017.05.058

• Umpolung
• gamma-Enolizable alpha,beta-unsaturated aldehydes
• Cross-dehydrogenative coupling
• Bronsted acids
• gamma-Regioselective

A direct gamma-regioselective nucleophilic addition of alcohols toward gamma-enolizable alpha,beta-unsaturated aldehydes was developed using a catalytic amount of MeSO3H (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 gamma-regio- and Ester eoselectivities.

• 出版日期2017-6-21