Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstraße 40, 48149 Münster, Germany.
J Am Chem Soc. 2022 Nov 9;144(44):20207-20213. doi: 10.1021/jacs.2c09248. Epub 2022 Oct 27.
Synthesis of bicyclic scaffolds has attracted growing interest because they are of high importance in modern pharmaceutical development. Here we report a strategy to access polysubstituted 2-oxabicyclo[2.1.1]hexanes in a single operation from readily accessible benzoylformate esters and bicyclo[1.1.0]butanes via visible-light-induced triplet energy transfer catalysis. The process is proposed to involve a formal [2π + 2σ] photocycloaddition/backbone C-H abstraction/aryl group migration sequence. A diverse range of (hetero)aryl groups successfully underwent migration to the backbone (C2) position to provide previously inaccessible bicyclic molecules, and the ester group of the product can serve as a handle for downstream manipulation, thus offering opportunities to rapidly build up molecular complexity and access new sp-rich chemical space.
双环支架的合成引起了越来越多的关注，因为它们在现代药物开发中具有重要意义。在这里，我们报告了一种策略，可通过可见光诱导的三重态能量转移催化，从易得的苯甲酰甲酸酯和二环[1.1.0]丁烷出发，一步合成多取代的 2-氧杂双环[2.1.1]己烷。该过程被认为涉及一个[2π + 2σ]光环加成/骨架 C-H 夺取/芳基迁移的序列。各种各样的（杂）芳基成功地迁移到骨架（C2）位置，提供了以前无法获得的双环分子，并且产物中的酯基可以作为后续操作的把手，从而为快速构建分子复杂性和进入新的富电子化学空间提供了机会。
