Catalytic asymmetric synthesis of nitrogen-containing chiral compounds using transition metal-diaminophosphine oxide catalyst systems

Abstract

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.

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