Excited‐State Copper Catalysis for the Synthesis of Heterocycles

Abstract

Heterocycles are one of the largest groups of organic moieties with significant medicinal, chemical, and industrial applications. Herein, we report the discovery and development of visible‐light‐induced, synergistic excited‐state copper catalysis using a combination of Cu(IPr)I as a catalyst and rac‐BINAP as a ligand, which produces more than 10 distinct classes of heterocycles. The reaction tolerates a broad array of functional groups and complex molecular scaffolds, including derivatives of peptides, natural products, and marketed drugs. Preliminary mechanistic investigation suggests in situ generations of [Cu(BINAP)2]+ and [Cu(IPr)2]+ catalysts that work cooperatively under visible‐light irradiation to facilitate catalytic carbo‐aroylation of unactivated alkenes, affording a wide range of useful heterocycles.

Two-in-one metallaphotoredox cross-couplings enabled by a photoactive ligand

“…98 In tandem with PPQN 2,4-di-OMe , copper was also catalytically viable for several metallaphotoredox reactions. With a common Cu(I) source (Cu(MeCN) 4 BF 4 ), the Cu + / PPQN 2,4-di-OMe -mediated radical addition to imine (63), 99 aromatic sulfonylation (53), [100][101][102] as well as alkene dicarbofunctionalization (65) 103 was performed Article successfully, which furnished the desired products accordingly (Figure 5; Equations 3, 4, and 5).…”