Catalyst-free photoinduced C(sp³)-C(sp³) bond formation through C-H insertions using non-activated alkanes/ethers

Among the various strategies to achieve C(sp³)-C(sp³) bond formation, the direct application of alkanes and ethers as coupling partners is an emerging and appealing method that circumvents the need for functionalized alkanes. However, it generally requires photocatalytic hydrogen atom transfer (HAT) coupled with nickel catalysis or multiple-step strategies. Herein, we report the direct C(sp³)-C(sp³) bond formation through C-H insertions using commercially available alkanes/ethers and N-tosylhydrazones under catalyst-free photoinduced conditions. This system is easy to operate and tolerates a diverse range of alkanes and ethers. Additionally, the one-pot reaction for directly coupling alkanes/ethers with aldehydes has also been developed. Furthermore, the gram-scale synthesis and the late-stage modifications demonstrated the potential of this strategy. The mechanism investigations demonstrated that the donor-type free carbene was generated under light irradiation, which then undergoes association and concerted insertion into C-H bonds of alkanes/ethers selectively to access C(sp³)-C(sp³) bond formation.