Sterically congested C–O and C–N bonds are ubiquitous in natural products, pharmaceuticals, and bioactive compounds. However, the development of a general method for the efficient construction of those sterically demanding covalent bonds still remains a formidable challenge. Herein, a photoredox-driven ring-opening C(sp³)–heteroatom bond formation of arylcyclopropanes is presented, which enables the construction of structurally diversified while sterically congested dialkyl ether, alkyl ester, alcohol, amine, chloride/fluoride, azide and also thiocyanate derivatives. The selective single electron oxidation of aryl motif associated with the thermodynamic driving force from ring strain-release is the key for this transformation. By this synergistic activation mode, C–C bond cleavage of otherwise inert cyclopropane framework is successfully unlocked. Further mechanistic and computational studies disclose a complete stereoinversion upon nucleophilic attack, thus proving a concerted S_N2-type ring-opening functionalization manifold, while the regioselectivity is subjected to an orbital control scenario.

空间拥挤的 C-O 和 C-N 键普遍存在于天然产物、药物和生物活性化合物中。然而，开发一种有效构建那些空间要求高的共价键的通用方法仍然是一项艰巨的挑战。在此，光氧化还原驱动的开环 C( sp ³)–芳基环丙烷的杂原子键形成，这使得能够构建结构多样化但空间拥挤的二烷基醚、烷基酯、醇、胺、氯/氟化物、叠氮化物以及硫氰酸酯衍生物。与环应变释放的热力学驱动力相关的芳基基序的选择性单电子氧化是这种转变的关键。通过这种协同活化模式，成功解锁了其他惰性环丙烷骨架的 C-C 键断裂。进一步的机理和计算研究揭示了亲核攻击时的完全立体倒置，从而证明了协同的 S _N 2 型开环官能化流形，而区域选择性受轨道控制方案的影响。