日本东京大学Shu Kobayashi团队报道了手性金属盐作为配体催化简单酰胺的不对称Mannich反应。 相关研究成果于2021年4月6日发表于国际一流学术期刊《美国化学会杂志》。

本文采用手性六甲基二硅肼钾（KHMDS）-双恶唑啉钾盐（K-Box）催化体系，研究了弱酸性单酰胺与亚胺的不对称Mannich反应。期望该反应能够持续进行以获得高产量与高非对映体和对映体选择性的目标化合物。

结果表明，K-烯醇盐与K-Box相互作用形成能与亚胺有效地反应的手性K-烯醇盐。在该体系中，K-Box（Box的钾盐）作为活性钾物种的手性配体。

附：英文原文

Title: Chiral Metal Salts as Ligands for Catalytic Asymmetric Mannich Reactions with Simple Amides

Author: Yasuhiro Yamashita, Aika Noguchi, Seiya Fushimi, Miho Hatanaka, Shu Kobayashi

Issue&Volume: April 6, 2021

Abstract: Catalytic asymmetric Mannich reactions of imines with weakly acidic simple amides were developed using a chiral potassium hexamethyldisilazide (KHMDS)–bis(oxazoline) potassium salt (K-Box) catalyst system. The desired reactions proceeded to afford the target compounds in high yields with high diastereo- and enantioselectivities. It was suggested that a K enolate interacted with K-Box to form a chiral K enolate that reacted with imines efficiently. In this system, K-Box (potassium salt of Box) worked as a chiral ligand of the active potassium species.

DOI: 10.1021/jacs.0c13317

Source: https://pubs.acs.org/doi/10.1021/jacs.0c13317