A visible-light-mediated radical addition of alkynoates to generate 3-bromocoumarins by using N-bromosuccinimide as the bromo source has been accomplished. This procedure provides a bromo radical addition/spirocyclization/ester migration cascade reaction under very mild reaction conditions without using any catalyst or strong oxidant and does not need high reaction temperature. Furthermore, the reaction can also be enlarged to the gram scale, and the product 3-bromocoumarins can be further applied in the synthesis of complex compounds.
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http://dx.doi.org/10.1039/c7ob02199b | DOI Listing |
Org 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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January 2025
Organic Chemistry Department, Faculty of Science, Autonomous University of Madrid, 28049 Madrid, Spain.
The functionalization of the C-N bond of amines is a straightforward strategy for the construction of complex scaffolds or for the late-stage functionalization of pharmaceuticals. Herein, we describe a photoredox-catalyzed strategy for the deaminative alkylation of primary amine-derived isonitriles that provides unnatural amino acid derivatives under mild conditions. The use of silacarboxylic acids as silyl radical precursors enables the generation of carbon-centered radicals that allow the construction of Csp-Csp bonds via a Giese-type addition, avoiding the undesired hydrodeamination product.
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January 2025
Southwest University, Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, 400715, Chongqing, CHINA.
A visible-light-mediated strategy is reported for the direct synthesis of polychlorinated vicinal diaryl alkanes from aryl alkenes and chloroform. In this approach, two haloalkyl radicals generated from chloroform via halogen atom transfer (XAT) and direct single electron transfer (SET) within the same photoredox catalysis cycle enable the 1,4-dichloromethyldimerization of alkenes. Besides chloroform, this strategy is applicable to carbon tetrachloride, bromotrichloromethane, and α-bromo carboxylic esters, yielding corresponding 1,4-disubstituted vicinal diaryl alkanes.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026, China.
The visible-light-mediated continuous dehydration condensation and oxidative radical dimerization, featuring sulfur hexafluoride (SF) as both a condensation agent and oxidant, have been developed. This photocatalytic method uses commercially available N-protected amino acids as substrates and enables the formation of azlactone monomers and dimers, facilitating efficient utilization and degradation of greenhouse gas SF.
View Article and Find Full Text PDFDalton Trans
December 2024
Environmental Engineering Division, Department of Civil Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.
Aquatic biota and human health are seriously threatened by the dramatic rise in antibiotics in environmental matrices. In this regard, the present study aims to improve knowledge of the combined effects of heterojunction design and defect engineering on the photocatalytic degradation of pharmaceuticals in aqueous matrices. Advantageously, the positioning of the valence band (VB) and conduction band (CB) levels of S@g-CN, being higher than those of BiMoO, demonstrates the feasibility of forming a type-II heterojunction between these materials.
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