Aryl nitriles are compounds with wide significance. They have made their own space in various sectors including pharmaceuticals, industries, natural product chemistry, and so on. Furthermore, they are also key intermediates in various transformations in organic chemistry. Transition metal-catalyzed cyanation reactions have proved to be a better replacement for the existing traditional synthetic strategies for aryl nitriles. Palladium is one of the most studied transition metals other than copper and nickel owing to its wide functional group compatibility and catalytic efficacy. There have been drastic developments in the field of palladium-catalyzed cyanation since its discovery in the 1973. This review summarizes the recent developments in the palladium-catalyzed cyanation of aryl halides and covers literature from 2012-2020.
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http://dx.doi.org/10.1039/d0ra05960a | DOI Listing |
J Org Chem
December 2024
School of Chemistry and Material Science and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, China.
Aryl nitriles are highly versatile and useful compounds. A palladium-catalyzed cyanation of diaryl sulfoxides using bench-stable Zn(CN) as the cyanating reagent has been developed. The reaction proceeded well using Pd(OAc) as the catalyst with the inexpensive ligand PCy in the presence of -BuONa.
View Article and Find Full Text PDFOrg Lett
May 2024
Department of Applied Chemistry, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan.
A denitrative cyanation of nitroarenes using organocyanides and a palladium catalyst was developed. The key for this reaction was the utilization of an aminoacetonitrile as a cyano source to avoid the generation of stoichiometric metal- and halogen-containing chemical waste. A wide range of nitroarenes, including heteroarenes and pharmaceutical molecules, can be converted into aryl nitriles.
View Article and Find Full Text PDFOrg Lett
May 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, Hangzhou 311121, China.
A Pd-catalyzed highly regio- and stereoselective hydrocyanation was developed, providing a novel approach to the stereodivergent synthesis of β-cyano-substituted acrylates in good yields with a wide substrate scope. The judicious selection of ligands was crucial for elegant control over the stereodivergence. Furthermore, the success of the -hydrocyanation hinges on the right matching of Pd and , which not only ensured the catalytic activity but also prevented the formation of α-cyanation products.
View Article and Find Full Text PDFNat Commun
March 2024
State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, 730000, Lanzhou, Gansu Province, China.
C-oligosaccharides are found in natural products and drug molecules. Despite the considerable progress made during the last decades, modular and stereoselective synthesis of C-oligosaccharides continues to be challenging and underdeveloped compared to the synthesis technology of O-oligosaccharides. Herein, we design a distinct strategy for the stereoselective and efficient synthesis of C-oligosaccharides via palladium-catalyzed nondirected C1-H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors while realizing the difunctionalization of 2-iodoglycals.
View Article and Find Full Text PDFOrg Lett
March 2024
School of Pharmaceutical Science and Technology, Hangzhou Institute for Advanced Study, Hangzhou, Zhejiang 310024, People's Republic of China.
Herein, we report the C-H cyanation of indoles a palladium-catalyzed directed C-CN activation reaction using aryl nitrile as a cyano source. The employment of the phenoxy-oriented group is the key to the cleavage of the C-CN bond. This protocol features a broad substrate scope, good efficiency, and high regioselectivity.
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