The development of practical approaches for the selective functionalization of strong, neutral C(sp³)–H bonds, such as those in petroleum-derived hydrocarbons, is of general interest but remains a remarkable challenge in synthetic chemistry. We here report a convenient approach that employs allyl bromides as the reagents and sodium fluoride as an activator in photochemical processes. Diverse C(sp³)–H functionalizations of alkanes, cycloalkanes and other relatively unreactive substances were enabled by using a stoichiometric or catalytic amount of allyl bromides as initiators in the presence of NaF, which furnished various allylated, heteroarylated, alkylated, hydrazinated and aminated products in good yields with high chemoselectivity and site selectivity. Binary NaF–allyl bromide adducts generated in situ appear to play essential roles in the reaction as light-active species, initiators for radical-mediated C–H cleavage and potential functionalization reagents. We expect that this transition-metal- and photosensitizer-free strategy will offer new opportunities for the C–H diversification of hydrocarbon feedstocks and the late-stage modification of lead compounds.

开发用于强中性 C( sp ³ )–H 键选择性功能化的实用方法，例如石油衍生碳氢化合物中的那些，引起了普遍的兴趣，但在合成化学中仍然是一个巨大的挑战。我们在这里报告了一种方便的方法，该方法使用烯丙基溴作为试剂，氟化钠作为光化学过程中的活化剂。多样的 C( sp ³)–H 官能化烷烃、环烷烃和其他相对不活泼的物质是通过在 NaF 存在下使用化学计量或催化量的烯丙基溴作为引发剂实现的，它以良好的收率提供各种烯丙基化、杂芳基化、烷基化、肼化和胺化产物高化学选择性和位点选择性。原位生成的二元 NaF-烯丙基溴化物加合物似乎在反应中作为光活性物质、自由基介导的 C-H 裂解的引发剂和潜在的功能化试剂发挥重要作用。我们预计这种不含过渡金属和光敏剂的策略将为碳氢化合物原料的 C-H 多样化和先导化合物的后期改性提供新的机会。