Affiliation:
1. 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 P. R. China
Abstract
AbstractDFT calculations have been applied to study the mechanisms of [3+2] and [3+2+1] reactions of ene/yne‐vinylcyclopropanes (shorted as ene/yne‐VCPs). The [3+2] reactions of ene/yne‐VCPs start from C−C cleavage of cyclopropane (CP cleavage) to form six‐membered rhodacycle, followed by alkene/alkyne insertion and reductive elimination. The [3+2+1] reactions have two competing pathways, one is the [3+2+1] pathway (CP cleavage, ene/yne insertion, CO insertion and reductive elimination) and the other is the [3+1+2] pathway (CP cleavage, CO insertion, ene/yne insertion and reductive elimination). The length of tether in substrates affects the ene/yne insertion steps in these cycloadditions, making some reactions fail or changing the reaction pathways. The reasons for these tether length effects are discussed.
Funder
National Natural Science Foundation of China
Subject
General Chemistry,Biochemistry,Organic Chemistry