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.
Abstract
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.
