Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2021 Jun 7;60(24):13671-13676. doi: 10.1002/anie.202102451. Epub 2021 May 7.
We report the synthesis of β-lactams from α-ketoacylsilanes and imines, which proceeds via a formal [2+2] photochemical cycloaddition with in situ generation of siloxyketene. This mild and operationally simple reaction proceeds in an atom-economic fashion with broad substrate scope, including aldimines, ketimines, hydrazones, and fused nitrogen heterocycles, affording a variety of important β-lactams with satisfactory diastereoselectivities in most cases. This reaction also features good functional-group tolerance, facile scalability and product diversification. Experimental and computational studies suggest that α-ketoacylsilanes can serve as photochemical precursors by engaging in a 1,3 silicon shift to the distal carbonyl group.
我们报告了β-内酰胺的合成方法，它是通过α-酮酰基硅烷和亚胺的形式[2+2]光化学环加成反应，同时原位生成硅氧基烯酮来实现的。该温和且操作简单的反应具有原子经济性，底物适用范围广泛，包括醛亚胺、酮亚胺、腙和稠合氮杂环，在大多数情况下以令人满意的非对映选择性提供了多种重要的β-内酰胺。该反应还具有良好的官能团耐受性、易于扩大规模和产物多样化的特点。实验和计算研究表明，α-酮酰基硅烷可以通过 1,3 硅迁移到远端羰基来作为光化学前体。
