We report a visible-light induced redox-neutral decarboxylative cross coupling reaction of indole-3-acetic acid NHPI esters with indoles using a Ru photosensitizer to deliver a wide range of symmetrical and unsymmetrical 3,3'-bisindolylmethane derivatives. Furthermore, the reaction is readily adapted to the preparation of a wide variety of diarylmethane derivatives.
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http://dx.doi.org/10.1021/acs.orglett.1c02523 | 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.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
Nucleophilic addition to α,β-unsaturated carbonyl compounds normally occurs at the carbonyl carbon or β-carbon. The direct α-nucleophilic addition at the α-carbon can hardly be achieved due to electronic mismatch. In this work, we report the nucleophilic addition of β-fluoroalkyl α-carbonyl carbocations that are prepared via -induced redox-neutral photocatalysis.
View Article and Find Full Text PDFChemistry
December 2024
Department of Chemistry and Pharmacy, University of Regensburg, Universitätstr. 31, 93053, Regensburg, Germany.
Herein, we report a mild photocatalytic redox-neutral dehydration of aryl-1,2-ethanediols forming the respective methyl ketones. In the proposed mechanistic cycle an initial hydrogen atom abstraction (HAT) is followed by a 1,2-spin center shift (SCS) as key steps. Interestingly, Eosin Y was found to act as a pre-catalyst dissociating into a catalytically active mixture under irradiation.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon 999077, Hong Kong (SAR), China.
Direct utilization of solar energy by semiconductor nanocrystals for chemical transformations via photocatalysis has recently drawn a great deal of attention. While most photocatalytic reactions are mediated through photoredox events, the ultimate reaction scalability relies on the use of sacrificial agents. The imbalanced population of photogenerated electrons and holes often leads to catalyst degradation through photocorrosion.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
We report the photocatalytic oxidation of α-carbonyl radicals of amides or esters to the corresponding α-carbonyl carbocations through super photoreductant CBZ6 induced redox-neutral photocatalysis. The α-carbonyl radicals are formed by the β-addition of alkyl radicals generated in situ by the photocatalytic fragmentation of N-hydroxyphthalimide esters to the α,β-unsaturated amides and esters. This method enables the α-nucleophilic addition of hydroxyl or alkoxyl radicals to amides and esters without any prefunctionalization.
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