キラルジアミノホスフィンオキシド類を配位子前駆体とする不斉遷移金属触媒反応の開発と応用
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This review describes the development of a new class of chiral secondary phosphine oxide preligands: Amino acid-derived P-chiral diaminophosphine oxides, DIAPHOXs, and their application to several transition metal-catalyzed asymmetric reactions. The Pd-DIAPHOX catalyst system was successfully applied to enantioselective construction of quaternary stereocenters through Pd-catalyzed asymmetric allylic alkylation with β-keto esters as prochiral nucleophiles, asymmetric allylic substitutions with nitromethane, asymmetric allylic amination with various substrates, and enantioselective synthesis of axially chiral allenes. Ir-catalyzed asymmetric allylic amination and alkylation of terminal allylic carbonates were also examined using structurally optimized DIAPHOX preligands, and the corresponding branched products were obtained in a highly regio- and enantioselective manner. Furthermore, the developed processes were successfully applied to the enantioselective synthesis of biologically active compounds.
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- キラルジアミノホスフィンオキシド類を配位子前駆体とする不斉遷移金属触媒反応の開発と応用