Investigation of the Carboxylate Position during the Acylation Reaction Catalyzed by Biaryl DMAP Derivatives with an Internal Carboxylate


  • We are grateful to Prof. Hendrik Zipse (Ludwig-Maximilians-Universität München) for valuable discussion on theoretical aspects for catalyst performance. This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Advanced Molecular Transformations by Organocatalysts” and a Grant-in-Aid for Scientific Research (C) from the Ministry of Education, Culture, Sports, Science and Technology (Japan). DMAP=4-dimethylaminopyridine.


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Location of the carboxylate ion: A series of biaryl DMAP catalysts with an internal carboxylate was prepared, and the catalytic activities of the derivatives were evaluated to determine the carboxylate position that most accelerated the DMAP-catalyzed acylation. The carboxylate ion proximal to the pyridine ring in a face-to-face geometry was found to act as an effective general base for the acylation reaction.