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The Regioselectivity of Bingel–Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes
Author(s) -
GarciaBorràs Marc,
Cerón Maira R.,
Osuna Sílvia,
Izquierdo Marta,
Luis Josep M.,
Echegoyen Luis,
Solà Miquel
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201509057
Subject(s) - metallofullerene , pentagon , regioselectivity , chemistry , computational chemistry , density functional theory , aromaticity , fullerene , molecule , organic chemistry , mathematics , geometry , catalysis
In this work, the Bingel–Hirsch addition of diethylbromomalonate to all non‐equivalent bonds of Sc 3 N@ D 3h ‐C 78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel–Hirsch reaction of Sc 3 N@ D 5h ‐C 80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes.