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Metal-catalyzed highly Markovnikov-type selective hydrofunctionalization of terminal alkynes provides a straightforward and atom-economical route to access 1,1-disubstituted alkenes, which have a wide range of applications in organic synthesis. However, the highly Markovnikov-type selective transformations are challenging due to the electronic and steric effects during the addition process. With the development of metal-catalyzed organic synthesis, different metal catalysts have been developed to solve this challenge, especially for platinum group metal catalysts. In this perspective, we review homogeneous metal-catalyzed Markovnikov-type selective hydrofunctionalization of terminal alkynes according to the classified element types as well as reaction mechanisms. Future avenues for investigation are also presented to help expand this exciting field.
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http://dx.doi.org/10.1039/d4cs00167b | DOI Listing |
Org Lett
November 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, China.
Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes presents a useful but challenging transformation due to the complex selectivity and multiple reaction pathways. We describe herein an unprecedented highly efficient and selective palladium-catalyzed hydrocyanation of methylenecyclopropanes to give various 2-substituted allylic nitriles. Mechanistic studies demonstrated that the transformation may undergo Markovnikov-type hydrometalation and β-carbon elimination.
View Article and Find Full Text PDFChem Soc Rev
July 2024
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310058, China.
Metal-catalyzed highly Markovnikov-type selective hydrofunctionalization of terminal alkynes provides a straightforward and atom-economical route to access 1,1-disubstituted alkenes, which have a wide range of applications in organic synthesis. However, the highly Markovnikov-type selective transformations are challenging due to the electronic and steric effects during the addition process. With the development of metal-catalyzed organic synthesis, different metal catalysts have been developed to solve this challenge, especially for platinum group metal catalysts.
View Article and Find Full Text PDFInorg Chem
January 2024
State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China.
Reductive ring-opening of epoxides is a green pathway for synthesizing highly value-added alcohols. In this study, we present a practically applicable approach for the synthesis of anti-Markovnikov-type alcohols with high yields from aliphatic and aromatic epoxides under mild conditions by developing porous metal silicate (PMS) catalysts. A PMS material PMS-20 consists of cobalt and nickel bimetal redox-active sites, exhibiting exceptional catalytic activity and selectivity in the reductive ring-opening of terminal epoxides with >99% yield of primary alcohols.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2023
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
The selective transition-metal catalyzed C-F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp )-F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed selective C(sp )-F bond alkylation of HFO-1234yf with alkylzinc reagents.
View Article and Find Full Text PDFJ Org Chem
February 2023
School of Chemistry and Materials Science, Ludong University, Yantai 264025, P. R. China.
A highly site-selective and Markovnikov-type radical C-H alkylation of purines with alkenes is achieved, allowing fast construction of the C(sp)-C(sp) bond at the C-6-position of purines and purine nucleosides using O as a green oxidant and alkenes as cheap alkylation reagents. The route was also a radical route to synthesize C-alkyl-N-substituted purines with potential steric hindrance between C-alkyl groups and N-substituted groups. This reaction is easily scaled up and has excellent functional group compatibility and broad substrate scopes.
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