The catalytic method features a cooperative interaction between Ni and Al imparting remote C-H alkenylation at the C5 position of imidazo[1,5-a]pyridine with alkynes at mild conditions. Exclusion of AlMe3 switches the selectivity to the C3 position. Reactions with styrene and other olefinic substrates affording C5-adducts by Ni/Al catalysis are also included.
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http://dx.doi.org/10.1021/ol502314p | DOI Listing |
Org Lett
January 2025
School of Chemical Sciences, National Institute of Science Education and Research (NISER) Bhubaneswar, An OCC of Homi Bhabha National Institute, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha 752050, India.
The temperature-dependent switching behavior of the saccharin radical is demonstrated, enabling the regiodivergent C-H and C-H functionalization of quinoxalin-2(1)-ones. The saccharin radical was generated through N-Br bond cleavage in -bromosaccharin (NBSA) and was observed to transition between radical and radicophile roles. At -10 °C, it was utilized as a radicophile, resulting in 100% C-amination, while at +35 °C, it acted as a radical, leading to exclusive C-bromination.
View Article and Find Full Text PDFJ Org Chem
January 2025
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004, China.
Among the known aromatic -heterocycles, pyrroles are significant and versatile privileged components in pharmacologically relevant molecules. Herein, we demonstrate a protocol for the selective construction of alkynylated pyrroles in a diversity-oriented fashion through divergent C2/C5 site-selective alkynylation of pyrrole derivatives by employing a palladium catalyst with two different solvent systems. In the presence of 1,4-dioxane, the C2-alkynylation process via chelation-assisted palladation is favored.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Chemical Biology of Fujian Province, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry and Biochemistry, Loyola University Chicago, Chicago, Illinois 60660, United States.
Angew Chem Int Ed Engl
December 2024
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, 2318 Yuhangtang Road, Hangzhou, 311121, P. R. China.
In industry, the two important nitrile starting materials, adiponitrile and 2-methylglutaronitrile, are primarily manufactured through the well-known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel-catalyzed divergent, one-step double hydrocyanation of 1,3-butadiene to produce either adiponitrile or 2-methylglutaronitrile in high regioselectivity.
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