A general and mild strategy involving three-component carboarylation of unactivated alkenes with protic C(sp)-H feedstocks via photoredox catalysis was reported. This catalytic system is compatible with a broad range of unactivated alkenes, cyano-substituted arenes, and diverse protic C(sp)-H feedstocks. The synthetic value of this protocol was demonstrated by the late-stage functionalization of complex molecules and the synthesis of the antiallergies including pheniramine, chlorpheniramine, and brompheniramine.
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http://dx.doi.org/10.1021/acs.orglett.2c03247 | DOI Listing |
Nat Commun
January 2025
Department of Dermatology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, Chengdu, China.
Unsymmetric disulfides are prevalent in natural products and are essential in medicinal chemistry and materials science, but their robust synthesis poses significant challenges. In this paper, we report an expeditous transition-metal-free methodology for synthesizing unsymmetric disulfides through the addition of perthiyl radicals to alkenes. This study marks the use of generating perthiyl radicals by reacting SO with unactivated alkyl (pseudo)halides (Cl/Br/I/OTs).
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
School of Chemistry, University College Dublin, Science Centre South, Dublin 4, Ireland.
We report a continuous flow approach generating bicyclic cyclobutanes from unactivated alkenes in a metal-free manner that is inspired by the Kochi-Salomon reaction. A filtered Hg-lamp in combination with a simple flow set-up and acetone as UV light-absorbing co-solvent are crucial for this method thus showcasing attractive features for further exploitations.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Chemistry and Chemical Engineering, Kunming University, Kunming, Yunnan 650214, P. R. China.
We report an electrophotocatalytic process that enables the thiocyanation and sulfonylation/cyclization of alkenes. It is applicable to a wide range of unactivated alkenes, using the inexpensive photocatalyst 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT) to produce a diverse array of heterocycles containing sulfonyl and thiocyano groups with good functional group tolerance. The protocol operates under mild, chemical oxidant- and transition-metal-free, with a broad scope of substrates.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Catalytic regio- and enantioselective hydroamination of less activated internal alkenes presents a challenge to synthetic chemists due to their low reactivity and the difficulty in simultaneously controlling regio- and enantioselectivities. Here, we report an iridium-catalyzed enantioselective hydroamination of internal alkenes directed by an amide. The amide group on the alkene effectively directs the catalyst to overcome the low reactivity and control the regioselectivity and the enantiotopic face selection.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Bio-Based Material Science and Technology, Ministry of Education, College of Material Science and Engineering, Northeast Forestry University, Harbin 150040, People's Republic of China.
A visible-light-induced method for the hydrodichloromethylation of unactivated alkenes using chloroform (CHCl) was developed, employing pyridine·BH as the halogen atom transfer (XAT) reagent. The strategy showed a broad functional group tolerance, and 29 examples of unactivated alkenes, including complex natural products or drug derivatives, have been established with good yields. Mechanistic studies indicated that CHCl serves as both the source of a dichloromethyl radical and a hydrogen atom transfer (HAT) reagent, and the borane short-chain reaction process was involved in this system.
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