瑞士联邦理工学院Nicolai Cramer研究团队报道了催化对映选择性还原Eschenmoser-Claisen重排。相关研究成果于2024年1月26日发表在《科学》。

对映选择性催化中的一个重要挑战是开发精确合成相邻拥挤的全碳季碳立体中心的策略。[3,3]-顺位重排的明确过渡态及其潜在的立体特异性使它们成为合成此类阵列的强大工具。然而，这种类型的周环反应仍然很难催化，尤其是以对映选择性的方式。

该文中，研究人员描述了手性1,3,2-二氮杂磷烯氢化物催化的对映选择性还原Eschenmoser-Claisen重排。这种发展的转化能够完全控制两个新形成的无环立体生成中心，生成具有相邻的全碳季-叔或季-季碳原子的酰胺。

附：英文原文

Title: Catalytic enantioselective reductive Eschenmoser-Claisen rearrangements

Author: Guoting Zhang, Matthew D. Wodrich, Nicolai Cramer

Issue&Volume: 2024-01-26

Abstract: An important challenge in enantioselective catalysis is developing strategies for the precise synthesis of neighboring congested all-carbon quaternary stereocenters. The well-defined transition states of [3,3]-sigmatropic rearrangements and their underlying stereospecificity render them powerful tools for the synthesis of such arrays. However, this type of pericyclic reaction remains notoriously difficult to catalyze, especially in an enantioselective fashion. Herein, we describe an enantioselective reductive Eschenmoser-Claisen rearrangement catalyzed by chiral 1,3,2-diazaphospholene-hydrides. This developed transformation enables full control of the two newly formed acyclic stereogenic centers, leading to amides with vicinal all-carbon quaternary-tertiary or quaternary-quaternary carbon atoms.

DOI: adl3369

Source: https://www.science.org/doi/10.1126/science.adl3369