A complementary oxidative photocatalytic strategy is presented. In the presence of 4‐nitroanisole, hexafluoroisopropanol (HFIP) as a proton source is activated and the proton photoreduction is enhanced, enabling a range of cyclizative aryltrifluoromethylations of alkenes and CF3SO2Na (Langlois’ reagent) with hydrogen evolution. Such a protocol is general, for both activated and unactivated olefins could be used as the substrates, affording a variety of CF3‐containing heterocycles such as indolines, indolin‐2‐ones, 3,4‐dihydroisoquinolin‐1‐ones, 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines, benzoimidazo[2,1‐a]isoquinolin‐6(5H)‐ones and 1,2,3,4‐tetrahydroisoquinolines, under mild and metal‐ and oxidant‐free conditions with a good functional‐group tolerance. Extensive mechanistic investigations revealed that p‐nitroanisole (p‐NA) does not react with the photocatalyst directly as an oxidant, but rather activates HFIP via proton‐coupled electron transfer (PCET) and scavenges some of the reduced protons to improve proton photoreduction.

A heat- or photoredox/iron dual catalysis-enabled dehydrogenative acylarylation of N-allyl anilines leading to 2-substituted 3-(α-acyl) indolines with a quaternary stereogenic center is presented, with unactivated alkenic bonds as radical acceptors...

A novel photocatalytic protocol for effective and efficient synthesis of cyclic 1,5-diketone containing chroman-4-one skeletons in moderate to good yields via radical cascade acylmethylation/cyclization of 2-(allyloxy)arylaldehydes with a-bromo ketones has...