Herein, we demonstrate a regioselective intramolecular C-N cross-coupling for the synthesis of 14-quinazolino[3,2-]phenanthridin-14-one by using 9-mesityl-10-methylacridinium perchlorate as the visible-light (450-470 nm) photocatalyst. The experiments with BHT, TEMPO, and Stern-Volmer quenching studies helped to rationalize a radical pathway a SET mechanism.
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http://dx.doi.org/10.1039/d3cc00537b | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Univ. Bordeaux, CNRS, Bordeaux INP, ISM UMR 5255, F-33400, Talence, France.
Polystyrene (PS) is a commodity plastic recalcitrant to chemical recycling or upcycling processes. Approaches aimed at deconstructing PS by photocatalytic means struggle to generate high-energy species capable of cleaving the robust C-H and C-C bonds of PS. We show that 9-mesityl-10-methylacridinium perchlorate (MA) is capable of upcycling various grades of PS substrates into up to 40 % benzoic acid (BAc), formic acid (FA) and small proportions of acetophenone (ACP), under visible light (456 nm) or through solar radiation.
View Article and Find Full Text PDFJ Org Chem
September 2024
Department of Chemistry, Birla Institute of Technology and Science, Pilani (BITS Pilani), Hyderabad Campus, Jawahar Nagar, Hyderabad 500078, Telangana, India.
Herein, we report a metal-free, organophotoredox-catalyzed sustainable C-H thiocyanation of a biologically active class of N-heterocycles, pyrazolo[1,5-]pyrimidines, with potassium thiocyanate (KSCN) using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst (PC) and molecular oxygen as the terminal oxidant under blue-light-emitting diode irradiation at room temperature. The developed catalytic protocol features mild reaction conditions, a broad substrate scope, a high yield of products, and a straightforward scalability. Mechanistic studies revealed a radical pathway involving reductive quenching of the PC by KSCN.
View Article and Find Full Text PDFJ Org Chem
February 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER) Bhubaneswar, An OCC of Homi Bhabha National Institute, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Bhubaneswar, Odisha 752050, India.
The atom transfer radical addition (ATRA) reaction is defined as a method for introducing halogenated compounds into alkenes via a radical mechanism. In this study, we present an ATRA approach for achieving regioselective functionalization of quinoxalin-2(1)-ones by activating C-Br bonds of CBr and subsequent trihaloalkyl-carbofunctionalization of styrenes employing the 9-mesityl-10-methylacridinium perchlorate (Fukuzumi) photocatalyst under 3W blue LED (450-470 nm) irradiation. This three-component radical cascade process demonstrates remarkable efficiency in the synthesis of 1-methyl-3-(3,3,3-tribromo-1-(4-chlorophenyl)propyl)quinoxalin-2(1)-one derivatives.
View Article and Find Full Text PDFJ Org Chem
July 2023
School of Chemical Sciences, National Institute of Science Education and Research (NISER) Bhubaneswar, An OCC of Homi Bhabha National Institute, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha 752050, India.
Herein we report a cascaded chalcogenation of aryl alkynoates or -arylpropynamides using 9-mesityl-10-methylacridinium perchlorate as a visible light photocatalyst to obtain selectively either 3-sulfenylated/selenylated coumarins or spiro[4,5]trienones. In a radical initiated process, the spiro-cyclization reaction was favored due to the presence of a -OMe or -F substituent at the para position of the aryl group, which helped to stabilize the allylic radical intermediate formed during the reaction. Otherwise, 6-endo-trig cyclization led to 3-sulfenylated/selenylated coumarins.
View Article and Find Full Text PDFChem Commun (Camb)
April 2023
School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of Homi Bhabha National Institute, Bhubaneswar, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha 752050, India.
Herein, we demonstrate a regioselective intramolecular C-N cross-coupling for the synthesis of 14-quinazolino[3,2-]phenanthridin-14-one by using 9-mesityl-10-methylacridinium perchlorate as the visible-light (450-470 nm) photocatalyst. The experiments with BHT, TEMPO, and Stern-Volmer quenching studies helped to rationalize a radical pathway a SET mechanism.
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