Affiliation:
1. Molecular Horizons and School of Chemistry and Molecular Bioscience University of Wollongong Wollongong New South Wales 2522 Australia
2. School of Natural Sciences Macquarie University North Ryde NSW 2109 Australia
Abstract
AbstractThe Rh(I)‐catalyzed denitrogenative annulation reactions of 1,2,3‐thiadiazoles are a new direct approach to synthesizing densely functionalized heterocycles. The synthesis of multisubstituted thiophenes is possible using this methodology, however the difficulty to predict which regioisomer will form is a current limitation. In this current work, systematic computational and experimental studies were performed addressing how the terminal alkyne substituent effects regioselectivity. The data revealed that the electronic and steric properties of the alkyne substituent effects regioselectivity, including whether the group is aryl or alkyl. The insight gained from this study has allowed the development of a framework for predicting regioselectivity for the Rh(I)‐catalyzed denitrogenative transannulation of 1,2,3‐thiadiazoles with terminal alkynes.
Subject
Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis