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逆氢化物穿梭催化实现复杂框架的立体选择性一步合成
作者:小柯机器人 发布时间:2022/10/23 13:12:20

奥地利维也纳大学Maulide Nuno团队报道了逆氢化物穿梭催化实现复杂框架的立体选择性一步合成。相关研究成果发表在2022年10月20日出版的《自然—化学》。

从简单的前体一步快速组装复杂的支架,从效率和可持续性的角度来看,这是一种理想的反应。事实上,尽管该学科取得了巨大进展,但复杂生物碱框架的直接单步合成仍然是有机化学核心领域的一个尚未解决的问题。

该文中,研究人员提出了一种基于反向氢化物穿梭催化概念,将动态组装的三元配合物转化为有价值的氮双环支架的广泛策略。三元配合物很容易由三种简单的前体原位构建,并且能够实现各种替代模式的高度模块化安装。经过独特的双催化系统后,过渡中间体经历了由氢化物供给引发的不寻常的氢化物穿梭过程。此外,研究还表明,结合不对称有机催化,产物生物碱框架具有优异的光学纯度。

附:英文原文

Title: Inverse hydride shuttle catalysis enables the stereoselective one-step synthesis of complex frameworks

Author: Klose, Immo, Di Mauro, Giovanni, Kaldre, Dainis, Maulide, Nuno

Issue&Volume: 2022-10-20

Abstract: The rapid assembly of complex scaffolds in a single step from simple precursors identifies as an ideal reaction in terms of efficiency and sustainability. Indeed, the direct single-step synthesis of complex alkaloid frameworks remains an unresolved problem at the heart of organic chemistry in spite of the tremendous progress of the discipline. Herein, we present a broad strategy in which dynamically assembled ternary complexes are converted into valuable azabicyclic scaffolds based on the concept of inverse hydride shuttle catalysis. The ternary complexes are readily constructed in situ from three simple precursors and enable a highly modular installation of various substitution patterns. Upon subjection to a unique dual-catalytic system, the transient intermediates undergo an unusual hydride shuttle process that is initiated by a hydride donation event. Furthermore, we show that, in combination with asymmetric organocatalysis, the product alkaloid frameworks are obtained in excellent optical purity.

DOI: 10.1038/s41557-022-00991-4

Source: https://www.nature.com/articles/s41557-022-00991-4

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex