TY - JOUR
T1 - Insights into the Mechanism of Anodic N-N Bond Formation by Dehydrogenative Coupling
AU - Gieshoff, Tile
AU - Kehl, Anton
AU - Schollmeyer, Dieter
AU - Moeller, Kevin D.
AU - Waldvogel, Siegfried R.
N1 - Funding Information:
T.G. is a recipient of a DFG fellowship by the Excellence Initiative by the Graduate School Materials Science in Mainz (GSC 266). The work done in the laboratories of K.D.M. was supported by the U.S. National Science Foundation (CHE-1463913). The support by The Advanced Lab for Electrochemistry and Electrosynthesis − ELYSION (Carl Zeiss Stiftung) and the DFG (WA 1276/17-1) is highly appreciated.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/9/6
Y1 - 2017/9/6
N2 - The electrochemical synthesis of pyrazolidine-3,5-diones and benzoxazoles by N-N bond formation and C,O linkage, respectively, represents an easy access to medicinally relevant structures. Electrochemistry as a key technology ensures a safe and sustainable approach. We gained insights in the mechanism of these reactions by combining cyclovoltammetric and synthetic studies. The electron-transfer behavior of anilides and dianilides was studied and led to the following conclusion: The N-N bond formation involves a diradical as intermediate, whereas the benzoxazole formation is based on a cationic mechanism. Besides these studies, we developed a synthetic route to mixed dianilides as starting materials for the N-N coupling. The compatibility with valuable functionalities like triflates and mesylates for follow-up reactions as well as the comparison of different electrochemical set-ups also enhanced the applicability of this method.
AB - The electrochemical synthesis of pyrazolidine-3,5-diones and benzoxazoles by N-N bond formation and C,O linkage, respectively, represents an easy access to medicinally relevant structures. Electrochemistry as a key technology ensures a safe and sustainable approach. We gained insights in the mechanism of these reactions by combining cyclovoltammetric and synthetic studies. The electron-transfer behavior of anilides and dianilides was studied and led to the following conclusion: The N-N bond formation involves a diradical as intermediate, whereas the benzoxazole formation is based on a cationic mechanism. Besides these studies, we developed a synthetic route to mixed dianilides as starting materials for the N-N coupling. The compatibility with valuable functionalities like triflates and mesylates for follow-up reactions as well as the comparison of different electrochemical set-ups also enhanced the applicability of this method.
UR - https://www.scopus.com/pages/publications/85028943923
U2 - 10.1021/jacs.7b07488
DO - 10.1021/jacs.7b07488
M3 - Article
C2 - 28792218
AN - SCOPUS:85028943923
SN - 0002-7863
VL - 139
SP - 12317
EP - 12324
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 35
ER -