The selective installation of boryl units at less-activated sites, which will facilitate easy access to a range of core structures embedded within bioactive molecules, is a longstanding challenge. Here, we show that catalytic amounts of an earth-abundant Fe(ii)-based complex promote efficient borylations at typically less-reactive positions vicinal (β) to common functional units. Utility is highlighted through the synthesis of drug-like scaffolds and regioconvergent transformation of olefin feedstock to value-added products bearing C_β–B stereogenic centres. These reactions proceed through tandem alkene isomerization followed by protoboration, and require that the in-situ-generated iron-hydride and iron-boryl catalysts function in synergy. By tuning the two processes of olefin transposition and protoboration, the present Fe-catalysed protocol can provide selective access to 1-boryl-, 2-boryl- or 3-borylalkane isomers. The insights gained from our studies are expected to advance general efforts towards unlocking selective functionalizations at other unactivated sites along the hydrocarbon chain.

长期以来，挑战是将硼烷基单元选择性地安装在较少活化的位点上，这将有助于容易地获得嵌入生物活性分子内的一系列核心结构。在这里，我们表明催化量的地球上大量的基于Fe（ii）的络合物可在通常反应性较低的邻位（β）到常见功能单元的位置促进有效的硼化作用。实用程序通过的类似药物的支架和烯烃原料的来增值产品轴承C regioconvergent变换合成强调_β–B立体感中心。这些反应通过串联烯烃异构化然后进行原硼酸酯化进行，并且要求原位生成的氢化铁和铁硼基催化剂起协同作用。通过调节烯烃转座和原硼烷化的两个过程，本铁催化的方案可以提供对1-硼烷基，2-硼烷基或3-硼烷基烷烃异构体的选择性访问。从我们的研究中获得的见识有望推动在烃链上其他未活化位点上实现选择性功能化的一般努力。