A novel, efficient and sustainable methodology involving visible-light-mediated construction of pyrazolo[4,3-]pyrimidin-7(6)-ones from easily available 4-amino-1-methyl-3-propyl-1-pyrazole-5-carboxamide and aldehydes in the presence of 4CzIPN under an oxygen atmosphere has been developed. This photocatalytic system worked under mild conditions and avoided the use of any excess amount of toxic oxidants and transition metals. A variety of functionalized products were obtained in good to excellent yields. Notably, the marketed drug sildenafil was successfully synthesized. In addition, a plausible reaction mechanism involving a radical process has been proposed and further applications of this protocol are under way in our laboratory.
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http://dx.doi.org/10.1039/d5ob00233h | DOI Listing |
Org Biomol Chem
March 2025
National & Local Joint Engineering Research Center for Mineral Salt Deep Utilization, Huaiyin Institute of Technology, Huaian 223003, China.
A novel, efficient and sustainable methodology involving visible-light-mediated construction of pyrazolo[4,3-]pyrimidin-7(6)-ones from easily available 4-amino-1-methyl-3-propyl-1-pyrazole-5-carboxamide and aldehydes in the presence of 4CzIPN under an oxygen atmosphere has been developed. This photocatalytic system worked under mild conditions and avoided the use of any excess amount of toxic oxidants and transition metals. A variety of functionalized products were obtained in good to excellent yields.
View Article and Find Full Text PDFDirect -difluoroallylation at the α-carbonyl position is a challenging process by conventional methods. Herein we report the photocatalytic radical α-C(sp)─H -difluoroallylation of amides with trifluoromethyl alkenes to access the target compounds with good yields and functional group tolerance. The mild and effective conditions allow -difluoroalkene motifs as carbonyl bioisosteres incorporated concisely to some complex molecules, including gemfibrozil and estrone derivatives, presenting great potential for late-stage functionalization of drugs, natural products, and bioactive intermediates.
View Article and Find Full Text PDFACS Appl Mater Interfaces
March 2025
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, India.
Covalent organic frameworks (COFs) serve as an outstanding platform for heterogeneous photocatalysis. We synthesized two analogous pyrene-based two-dimensional COFs with π-conjugated networks, one linked by C═N bonds and the other by C═C bonds, through Schiff base and Knoevenagel condensation reactions, respectively. We investigated the impact of these linkages on the photocatalytic activity of these COFs, using visible-light-mediated thioesterification as a model reaction.
View Article and Find Full Text PDFACS Appl Nano Mater
January 2025
Department of Physics, University of Cagliari, Complesso Universitario di Monserrato S.P. Monserrato-Sestu Km 0, 700 09042 Monserrato (CA), Italy.
Dual-functional photocatalysts help to maximize resource utilization in water remediation, but often they are visible-light-inactive, toxic, and cost-intensive. Herein, a type-II heterojunction visible-light-active photocatalyst is reported for tandem degradation of Rhodamine B and generation of H. A Rhodamine B degradation rate of 2.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Thiruvananthapuram 695551, Kerala, India.
Herein, we report a formal C-C bond azidation and cyanation of unactivated aliphatic ketones using commercially available tosyl azide and cyanide, respectively. A visible-light-mediated organophotocatalyst enables radical azidation and cyanation of ketone-derived pro-aromatic dihydroquinazolinones (under mostly redox-neutral conditions) as supported by preliminary mechanistic studies. These metal-free and scalable protocols can be used to synthesize tertiary, secondary, and primary alkyl azides and nitriles with good functional group tolerance and postsynthetic diversification of the azide group, including bioconjugation.
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