反応と合成の進歩シンポジウム 発表要旨概要
第32回反応と合成の進歩シンポジウム
セッションID: 2O08
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遷移金属―ジアミノホスフィンオキシド触媒系を用いる含窒素キラル化合物の触媒的不斉合成
*根本 哲宏坂本 達郎福山 尚山本 絵理濱田 康正
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In this presentation, we hope to report two types of transition metal-mediated asymmetric reactions using P-chirogenic diaminophosphine oxides (DIAPHOX). First, a general and highly enantioselective synthesis of cyclic aza-Morita-Baylis-Hillman (aza-MBH) reaction products is presented. Cyclic aza-MBH reaction products was obtained in excellent yield with up to 99% ee, and could be converted into various chiral synthetic fragments such as cyclic beta-amino acid derivatives. An Ir-catalyzed asymmetric allylic amination using chiral diaminophosphine oxide is also reported. Asymmetric allylic amination of terminal allylic carbonates proceeded in the presence of 2 mol % of Ir catalyst, 2 mol % of chiral diaminophosphine oxide, 5 mol % of sodium hexafluorophosphate, and BSA, affording the chiral branched allylic amines in up to 95% ee.
fig.1 Fullsize Image
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© 2006 日本薬学会
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