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.
Investigation of the Carboxylate Position during the Acylation Reaction Catalyzed by Biaryl DMAP Derivatives with an Internal Carboxylate†
Article first published online: 6 MAY 2013
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 52, Issue 25, pages 6445–6449, June 17, 2013
How to Cite
Nishino, R., Furuta, T., Kan, K., Sato, M., Yamanaka, M., Sasamori, T., Tokitoh, N. and Kawabata, T. (2013), Investigation of the Carboxylate Position during the Acylation Reaction Catalyzed by Biaryl DMAP Derivatives with an Internal Carboxylate . Angew. Chem. Int. Ed., 52: 6445–6449. doi: 10.1002/anie.201300665
- Issue published online: 11 JUN 2013
- Article first published online: 6 MAY 2013
- Manuscript Revised: 18 MAR 2013
- Manuscript Received: 25 JAN 2013
- Ministry of Education, Culture, Sports, Science and Technology (Japan)
- base catalysis;
- ion pairs;
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.