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Reaction Mechanism and Regioselectivity of the Bingel–Hirsch Addition of Dimethyl Bromomalonate to La@ C 2 v ‐C 82
Author(s) -
Martínez Juan Pablo,
GarciaBorràs Marc,
Osuna Sílvia,
Poater Jordi,
Bickelhaupt F. Matthias,
Solà Miquel
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504668
Subject(s) - regioselectivity , adduct , chemistry , derivative (finance) , computational chemistry , reaction mechanism , double bond , stereochemistry , medicinal chemistry , organic chemistry , catalysis , financial economics , economics
We quantum chemically explore the thermodynamics and kinetics of all 65 possible mechanistic pathways of the Bingel–Hirsch addition of dimethyl bromomalonate to the endohedral metallofullerene La@ C 2 v ‐C 82 that result from the combination of 24 nonequivalent carbon atoms and 35 different bonds present in La@ C 2 v ‐C 82 by using dispersion‐corrected DFT calculations. Experimentally, this reaction leads to four singly bonded derivatives and one fulleroid adduct. Of these five products, only the singly bonded derivative on C23 could be experimentally identified unambiguously. Our calculations show that La@ C 2 v ‐C 82 is not particularly regioselective under Bingel–Hirsch conditions. From the obtained results, however, it is possible to make a tentative assignment of the products observed experimentally. We propose that the observed fulleroid adduct results from the attack at bond 19 and that the singly bonded derivatives correspond to the C2, C19, C21, and C23 initial attacks. However, other possibilities cannot be ruled out completely.