Affiliation:
1. Department of Chemistry Renmin University of China Beijing 100872 China
2. Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry Peking University Beijing 100871 China
Abstract
AbstractWe report here computational evidence for a metalla‐Claisen rearrangement (MCR) in the case of gold‐catalyzed [4+2] cycloaddition reaction of yne‐dienes. The [4+2] reaction starts from exo cyclopropanation, followed by MCR and reductive elimination. The cyclopropane moiety formed in the first step is crucial for a low barrier of the MCR step. In addition, the importance of an appropriate combination of the tether group and the terminal substituent on alkyne in the yne‐diene substrates was studied. The mechanism of rhodium‐catalyzed [4+2] reaction of yne‐dienes was also investigated to see whether an MCR mechanism is involved or not. The findings and new understanding hereby reported represent an important advance in the catalysis field.
Funder
National Natural Science Foundation of China