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利用双功能亚硫亚胺从烯烃出发合成多种含氮杂环
作者:小柯机器人 发布时间:2022/7/28 12:40:06

近日,德国亚琛工业大学Tobias Ritter及其研究团队利用双功能亚硫亚胺,成功实现从烯烃出发合成多种含氮杂环。相关论文于2022年7月25日发表在《自然-化学》杂志上。

在该研究中,小组报道了利用亚硫亚胺作为双功能含氮自由基前体与烯烃的环化反应,该反应通过光氧化还原催化在一步内产生N-基无保护的杂环。结构多样的亚硫亚胺可以一步合成,然后与烯烃反应,得到有合成价值的五元、六元和七元杂环。试剂的双功能特性使自由基-极性交叉环化能够实现,从而使该反应具有广泛而多样的范围,这使其区别于所有其他以N原子为中心的自由基反应。与目前可得的其他单环合成方法相比,模块化合成亚硫亚胺可以获得更大结构多样性的含氮杂环产物。

研究人员表示,含氮分子在烯烃侧基上的分子内环化是构建含氮杂环的一种有效策略,在制药和材料等领域具有至关重要的作用。然而,分子间类似的环化反应对于含氮砌块(包括以N原子为中心的自由基)来说更为少见,并且发散的和模块化的版本此前从未被建立过。

附:英文原文

Title: Bifunctional sulfilimines enable synthesis of multiple N-heterocycles from alkenes

Author: Cheng, Qiang, Bai, Zibo, Tewari, Srija, Ritter, Tobias

Issue&Volume: 2022-07-25

Abstract: Intramolecular cyclization of nitrogen-containing molecules onto pendant alkenes is an efficient strategy for the construction of N-heterocycles, which are of paramount importance in, for example, pharmaceuticals and materials. Similar intermolecular cyclization reactions, however, are scarcer for nitrogen building blocks, including N-centred radicals, and divergent and modular versions are not established. Here we report the use of sulfilimines as bifunctional N-radical precursors for cyclization reactions with alkenes to produce N-unprotected heterocycles in a single step through photoredox catalysis. Structurally diverse sulfilimines can be synthesized in a single step, and subsequently engage with alkenes to afford synthetically valuable five-, six- and seven-membered heterocycles. The broad and diverse scope is achievable by a radical-polar crossover annulation enabled by the bifunctional character of the reagents, which distinguishes itself from all other N-centred-radical-based reactions. The modular synthesis of the sulfilimines allows for larger structural diversity of N-heterocycle products than is currently achievable with other single cyclization methods.

DOI: 10.1038/s41557-022-00997-y

Source: https://www.nature.com/articles/s41557-022-00997-y

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