C(sp³)-rich bicyclic hydrocarbon scaffolds, as exemplified by bicyclo[1.1.1]pentanes, play an increasingly high-profile role as saturated bioisosteres of benzenoids in medicinal chemistry and crop science. Substituted bicyclo[2.1.1]hexanes (BCHs) are emerging bicyclic hydrocarbon bioisosteres for ortho- and meta-substituted benzenes, but are difficult to access. Therefore, a general synthetic route to BCHs is needed if their potential as bioisosteres is to be realized. Here we describe a broadly applicable catalytic approach that delivers substituted BCHs by intermolecular coupling between olefins and bicyclo[1.1.0]butyl (BCB) ketones. The SmI₂–catalysed process works for a wide range of electron-deficient alkenes and substituted BCB ketones, operates with SmI₂ loadings as low as 5 mol% and is underpinned by a radical relay mechanism that is supported by density functional theory calculations. The product BCH ketones have been shown to be versatile synthetic intermediates through selective downstream manipulation and the expedient synthesis of a saturated hydrocarbon analogue of the broad-spectrum antimicrobial, phthalylsulfathiazole.

以双环 [1.1.1] 戊烷为例，富含 C( sp 3 ) 的双环碳氢化合物骨架在药物化学和作物科学中作为苯系物的饱和生物电子等排体发挥着越来越引人注目的作用^。取代双环 [2.1.1] 己烷 (BCH) 是邻位和间位取代苯的新兴双环烃生物电子等排物，但难以获得。因此，如果要实现生物安全信息交换所作为生物电子等排体的潜力，就需要一条通用的生物安全信息交换所合成路线。在这里，我们描述了一种广泛适用的催化方法，该方法通过烯烃和双环 [1.1.0] 丁基 (BCB) 酮之间的分子间偶联提供取代的 BCH。SmI ₂–催化过程适用于范围广泛的缺电子烯烃和取代的 BCB 酮，在低至 5 mol% 的SmI _{2负载下运行，并以自由基中继机制为基础，该机制得到密度泛函理论计算的支持。}通过选择性下游操作和广谱抗菌剂邻苯二甲酰磺胺噻唑的饱和烃类似物的便捷合成，BCH 酮产品已被证明是一种多功能合成中间体。