Photoredox Annulation of Polycyclic Aromatic Hydrocarbons.

The rise of interest in using polycyclic aromatic hydrocarbons (PAHs) and molecular graphenoids in optoelectronics has recently stimulated the growth of modern synthetic methodologies giving access to intramolecular aryl-aryl couplings. Here, we show that a radical-based annulation protocol allows expansion of the planarization approaches to prepare functionalized molecular graphenoids. The enabler of this reaction is peri-xanthenoxanthene, the photocatalyst which undergoes photoinduced single electron transfer with an ortho-oligoarylenyl precursor bearing electron-withdrawing and nucleofuge groups. Dissociative electron transfer enables the formation of persistent aryl radical intermediates, the latter undergoing intramolecular C-C bond formation, allowing the planarization reaction to occur. The reaction conditions are mild and compatible with various electron-withdrawing and -donating substituents on the aryl rings as well as heterocycles and PAHs. The method could be applied to induce double annulation reactions, allowing the synthesis of π-extended scaffolds with different edge peripheries.

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

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.