Oxidation of N-Alkyl(iso)quinolinium Salts Over TEMPO@Metal-Organic Framework Heterogeneous Photocatalyst†

Shan-Shan Fu; Qiang-Qiang Yuan; Lihua Ma; Zhi-Ming Zhang; Tong-Bu Lu; Song Guo

doi:10.1002/cssc.202202163

Oxidation of N-Alkyl(iso)quinolinium Salts Over TEMPO@Metal-Organic Framework Heterogeneous Photocatalyst^†

ChemSusChem. 2023 Mar 22;16(6):e202202163. doi: 10.1002/cssc.202202163. Epub 2023 Jan 20.

Authors

Shan-Shan Fu^{1

2}, Qiang-Qiang Yuan¹, Lihua Ma^{1

3}, Zhi-Ming Zhang¹, Tong-Bu Lu¹, Song Guo¹

Affiliations

¹ MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, Tianjin University of Technology, Tianjin, 300384, China.
² College of Chemistry and Chemical Engineering, Key Laboratory of Fine Chemicals of College of Heilongjiang Province, Qiqihar University, Qiqihar, 161006, China.
³ School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, 150001, China.

PMID: 36545816
DOI: 10.1002/cssc.202202163

Abstract

Quinolones and isoquinolones are of particular importance to pharmaceutical industry due to their diverse biological activities. However, their synthetic protocols were limited by high toxicity, high energy consumption, poor functional group tolerance and noble metal catalyst. This study concerns the development of a series of TEMPO@PCN-222 (TEMPO: 2,2,6,6-tetramethylpiperidinyl-1-oxy; PCN: porous coordination network) composite photocatalysts by coordinating different amount of 4-carboxy-TEMPO with the secondary building units of PCN-222. Upon visible-light irradiation, photogenerated holes in the highest occupied molecular orbital of PCN-222 can smoothly transfer to TEMPO, which can significantly boost the photosynthesis of bioactive (iso)quinolones from readily available N-alkyl(iso)quinolinium salts. TEMPO@PCN-222 exhibits an outstanding catalytic stability and substrate tolerance with a 1-methyl-2-quinolinone yield of 86.7 %, over four times that with PCN-222 (21.4 %). This work provides a new route to construct composite photocatalysts from abundant starting materials for efficient photosynthesis of high value-added chemicals.

Keywords: heterogeneous catalysis; metal-organic frameworks; oxidation; photocatalysis; photoredox.

Abstract

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