Photoreduction of Anthracenes Catalyzed by peri-Xanthenoxanthene: a Scalable and Sustainable Birch-Type Alternative

Abstract

The typical Birch reduction transforms arenes into cyclohexa-1,4-dienes by using alkali metals, an alcohol as a proton source, and an amine as solvent. Capitalizing on the strong photoreductive properties of peri-xanthenoxanthene (PXX), herein we report the photocatalyzed “Birch-type” reduction of acenes by employing visible blue light irradiation at room temperature in the presence of air. Upon excitation at 405 or 460 nm in the presence of a mixture of N,N-diisopropylethylamine (DIPEA) and trifluoromethanesulfonimide (HNTf2) in DMSO, PXX photocatalyzes the selective reduction of full-carbon acene derivatives (24–75 %). Immobilization of PXX onto polydimethylsiloxane (PDMS) beads (PXX-PDMS) allowed the use of the catalyst in heterogeneous batch reactions, giving 9-phenyl-9,10-dihydroanthracene in high yield (68 %). The catalyst could easily be recovered and reused, with no notable drop in performance observed after five reaction cycles. Integration of the PXX-PDMS beads into a microreactor enabled the reduction of acenes under continuous-flow conditions, thereby validating the sustainability and scalability of this heterogeneous-phase approach.