Photocatalytic C(sp<sup>3</sup>)–O/N Cross-Couplings by NaI–PPh<sub>3</sub>/CuBr Cooperative Catalysis: Computational Design and Experimental Verification
Run‐Han Li, Yu‐Long Zhao, Qingkun Shang, Yun Geng, Xinlong Wang, Zhong‐Min Su, Guangfu Li, Wei Guan
Abstract
Photocatalytic coupling reactions have developed rapidly in the field of organic synthesis. However, highly efficient, broad-spectrum, low-cost, and energy-saving catalytic systems are urgently needed. Herein a desirable alternative combining NaI–PPh3 photoredox catalyst and Cu(I) catalyst was theoretically designed and evaluated from photophysical processes and potential energy surfaces. This metallaphotoredox catalysis could achieve C(sp3)–O/N cross-couplings of alkyl N-hydroxyphthalimide esters with phenols/secondary amines via a radical mechanism merging photoexcited radical decarboxylation and a low-valent CuI–CuII–CuI cycle. More importantly, a series of target reactions can be realized with high yield (≥90%) at room temperature under only irradiation with 10 W blue light-emitting diodes for 4 h without additional precious photocatalysts, which is mild, convenient, and environmentally friendly. Thus, this synthesis strategy combining theory and experiment can provide a facile and economic route and a clear mechanistic understanding for C(sp3)–X cross-coupling reactions.