Microtubing-Reactor-Assisted Aliphatic C-H Functionalization with HCl as a Hydrogen-Atom-Transfer Catalyst Precursor in Conjunction with an Organic Photoredox Catalyst

Chlorine radical, which is classically generated by the homolysis of Cl-2 under UV irradiation, can abstract a hydrogen atom from an unactivated C(sp(3))-H bond. We herein demonstrate the use of HCl as an effective hydrogen-atom-transfer catalyst precursor activated by an organic acridinium photoredox catalyst under visible-light irradiation for C-H alkylation and allylation. The key to success relied on the utilization of microtubing reactors to maintain the volatile HCl catalyst. This photomediated chlorine-based C-H activation protocol is effective for a variety of unactivated C(sp(3))-H bond patterns, even with primary C(sp(3))-H bonds, as in ethane. The merit of this strategy is illustrated by rapid access to several pharmaceutical drugs from abundant unfunctionalized alkane feedstocks.