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Palladium Catalyzed Cyanation of Diaryl Sulfoxides.

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.

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Palladium-Catalyzed Denitrative Synthesis of Aryl Nitriles from Nitroarenes and Organocyanides.

Org 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.

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Palladium-Catalyzed Hydrocyanation of Ynoates: En Route to the Stereodivergent Synthesis of β-Cyanated α,β-Unsaturated Esters via Ligand Controlled Regio- and Stereoselectivity.

Org 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.

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Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals.

Nat 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.

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Palladium-Catalyzed Directed Carbon-Carbon Bond Activation of Aryl Nitriles for Cyano Transfer.

Org 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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