Room-Temperature ortho-Alkoxylation and -Halogenation of N-Tosylbenzamides by Using Palladium(II)-Catalyzed CH Activation

• Published in: Chemistry : a European journal 2014-06, Vol.20 (24), p.7507-7513
• Main Authors: Péron, Florent, Fossey, Christine, Sopkova-de Oliveira Santos, Jana, Cailly, Thomas, Fabis, Frédéric
• Format: Article
• Language: English
• Subjects: Activation; alkoxylation; Aromatic compounds; Catalysis; Chemical Sciences; CH activation; Functional groups; Halogenation; Methodology; Molecular Structure; Organic chemistry; Oxidants; Palladium; Palladium - chemistry; Stereoisomerism; synthetic methods; Transformations
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201303923

The N‐tosylcarboxamide group can direct the room‐temperature palladium‐catalyzed CH alkoxylation and halogenation of substituted arenes in a simple and mild procedure. The room‐temperature stoichiometric cyclopalladation of N‐tosylbenzamide was first studied, and the ability of the palladacycle to react with oxidants to form CX and CO bonds under mild conditions was demonstrated. The reaction conditions were then adapted to promote room‐temperature ortho‐alkoxylations and ortho‐halogenations of N‐tosylbenzamides using palladium as catalyst. The scope and limitation of both alkoxylations and halogenations was studied and the subsequent functional transformation of the N‐tosylcarboxamide group through nucleophilic additions was evaluated. This methodology offers a simple and mild route to diversely functionalized arenes. Mild method for diverse arenes: Room‐temperature palladium‐catalyzed ortho‐alkoxylations and ortho‐halogenations of N‐tosylbenzamides are described. Along with the ability of the N‐tosylcarboxamide group to be transformed in useful functional groups, this methodology offers a simple and mild route to diversely functionalized arenes (see scheme).