Related Experiment Video
Updated: May 14, 2026

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)
Published on: January 17, 2020
Bingel-Hirsch addition on endohedral metallofullerenes: kinetic versus thermodynamic control
Núria Alegret1, Antonio Rodríguez-Fortea, Josep M Poblet
1Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, c/Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
Abstract:
An extensive theoretical study of the Bingel-Hirsch addition of bromomalonate on scandium nitride endohedral fullerenes has been carried out. The prototypical and highly symmetrical Sc3N@I(h)-C80, with a structure that satisfies the isolated pentagon rule (IPR), and the non-IPR Sc3N@D3(6140)-C68 fullerene show analogous reaction paths despite the distinct topology of the carbon networks and different rotation freedom of the internal nitride cluster. For the two metallofullerenes, our results predict that the reaction takes place under kinetic control yielding open-cage fulleroids on [6,6] bonds, which is in good agreement with experimental data. The theoretical studies also show that predicting the reactivity of endohedral metallofullerenes is not straightforward and often an accurate analysis of the potential energy surface is required.
Related Concept Videos
Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control
Cycloaddition Reactions: MO Requirements for Thermal Activation
Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are formed faster owing to...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

