Alkanes in Minisci-Type Reaction under Photocatalytic Conditions with Hydrogen Evolution

We report herein a protocol for the selective activation of C(sp3)–H bonds based on the interplay of two readily available organic catalysts and their successful implementation in cross-coupling azaarenes with alkanes. This Minisci-like reaction is promoted by visible light at room temperature and is free from chemical oxidants, metals, and chlorinated solvents. A wide range of substrates are compatible, including some bioactive molecules. Mechanistic studies support a dual catalytic cycle with H2 evolution.This work was financially supported by the Generalitat Valenciana (SEJIGENT/2021/005 and IDIFEDER/2021/13) and the University of Alicante (GRE20-03-A granted to I. B.)

Metal- and chlorine-free cross-dehydrogenative coupling of azaarenes with alkanes without sacrificial oxidants.

Minisci-like cross-dehydrogenative coupling of azaarenes with unactivated alkanes offers an appealing approach to bioactive alkyl-substituted heterocycles from abundant feedstocks. Traditionally, this net oxidative C-C bond formation process uses sacrificial chemical oxidants with the consequent waste generation. Here we report a chemical oxidant-free solution for this transformation, promoted by visible light at room temperature in the absence of metals and chlorinated solvents. The reaction relies on the interplay of a readily available 9-arylacridine and inexpensive pyridine N-oxide as pre-catalysts. A wide range of azaarenes and C(sp3)-H partners are compatible with this protocol, which was applied to the late-stage functionalization of bioactive molecules and the gram-scale synthesis of one API intermediate using flow technology. Preliminary mechanistic studies support the dual catalytic cycle with H2 evolution

Alkanes in Minisci-Type Reaction under Photocatalytic Conditions with Hydrogen Evolution

We report herein a protocol for the selective activation of C(sp3)–H bonds based on the interplay of two readily available organic catalysts and their successful implementation in cross-coupling azaarenes with alkanes. This Minisci-like reaction is promoted by visible light at room temperature and is free from chemical oxidants, metals, and chlorinated solvents. A wide range of substrates are compatible, including some bioactive molecules. Mechanistic studies support a dual catalytic cycle with H2 evolution