Heck-Matsuda Arylation of Olefins Through a Bicatalytic Approach: Improved Procedures and Rationalization

• Published in: Advanced synthesis & catalysis Vol. 356; no. 5; pp. 1065 - 1071
• Main Authors: Oger, Nicolas, Le Callonnec, François, Jacquemin, Denis, Fouquet, Eric, Le Grognec, Erwan, Felpin, François-Xavier
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 24.03.2014; WILEY‐VCH Verlag; Wiley-VCH Verlag
• Subjects: Aniline; anilines; arenediazonium salts; Byproducts; Catalysis; Catalysts; Chemical Sciences; Deactivation; Electronics; Heck-Matsuda reaction; Methyl alcohol; Olefins; palladium; sustainable chemistry
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201301144

The scope of the palladium‐catalyzed Heck–Matsuda reaction, proceeding through the catalytic activation of anilines into the corresponding diazonium salts, has been considerably extended and is now working with deactivated electrophiles. Two different procedures, using catalytic amounts of both palladium and acid, have been optimized allowing the concept of bicatalysis to cover the complete electronic range of anilines. These environmentally friendly procedures proceed under very mild conditions, at room temperature in methanol, and only generate tert‐butyl alcohol, water and nitrogen as by‐products. Rationalization of reaction outcomes encountered in this work has been discussed with the support of computational studies.