反応と合成の進歩シンポジウム 発表要旨概要
第30回反応と合成の進歩シンポジウム
セッションID: 1O-14
会議情報

口頭発表
光学活性ジアミノホスフィンオキシド配位子の開発とPd触媒を用いる不斉4級炭素構築反応への展開
*根本 哲宏増田 貴政松本 貴義人見 牧福田 友昭濱田 康正
著者情報
会議録・要旨集 フリー

詳細
抄録
We developed a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. These chiral ligands were prepared from aspartic acid, and applied to Pd-catalyzed asymmetric allylic substitution. In addition to asymmetric allylic alkylation and amination of allyl acetate 6, Pd-catalyzed asymmetric allylic substitution with various β-keto esters was proceeded in the presence of Zn(OAc)2 to provide the corresponding products with a quaternary carbon in up to 94% ee. Allyl acetates conjugated with a ketone (11) or an ester group (12) were also applicable to this catalyst system, affording the products 15 and 16 with high enentioselectivity. Mechanistic studies indicated that two ligand molecules, which were generated in situ by BSA-induced tautomerization of diaminophosphine oxides, coordinated to Pd metal in a monodentate fashion, resulting in the formation of the catalytically active Pd complex (Pd:ligand = 1:2).
Scheme 1 Fullsize Image
著者関連情報
© 2004 日本薬学会
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