Selective Reactions of β-Ketocarbonyl Derivatives at γ-Positions: Control of Reaction Sites and Product Stereochemistries through Aminocatalysis

抄録

Development of γ-position-selective bond formation reactions of β-ketocarbonyl derivatives catalyzed by amine-based catalyst systems and reaction-based mechanistic analyses of the regioselective reactions are discussed. The reactions developed include enantioselective γ-position-selective Mannich reactions of β-ketoesters, β-ketophosphonates, and other β-ketocarbonyl derivatives to afford δ-amino β-ketocarbonyl derivatives and γ-position-selective formal aldol condensation reactions of β-ketophosphonates to afford γ,δ-unsaturated β-ketophosphonates. By harnessing the dynamics of the reversible formation of the enamines and/or the α-position-reacted products of β-ketocarbonyl derivatives, γ-position-selective bond formation reactions of β-ketocarbonyl derivatives under aminocatalysis were enabled.

グラフィカル アブストラクト