有機銅-ルイス酸複合剤の最近の展開

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Recent progress of our research about organocopper-Lewis acid complexes is summarized. The reaction of cyanocopper-boron trifluoride complexes with γ-mesyloxy-α, β-unsaturated esters gives α-alkylated-β, γ-unsaturated esters with very high 1, 3-chiral transfer (>99 : 1). In contrast, the reaction of γ-benzyloxy-α, β-unsaturated esters with various organocopper reagents proceeds in a 1, 4-addition manner to give the β-alkylated product. The diastereoselec-tivity is controlled by geometry of the carbon-carbon double bond. The diastereoselectivity in the reaction of γ-alkyl-α, β-unsaturated esters and related Michael acceptors highly depends upon the types of copper reagents. The syn-diastereoselectivity is observed with reagents which possess relatively high oxidation potential;cuprates or higher order cuprates produce the syn-diastereoselectivity. The anti-diastereoselectivity, which is expected from an ordinary Felkin-Anh model, is observed with the reagents having lower oxidation potential.
社団法人日本油化学会の論文