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Probing the Regioselectivity with Encapsulated H 2 : Diels–Alder Reaction of an Open‐Cage C 60 Derivative with Anthracene
Author(s) -
Hashikawa Yoshifumi,
Murata Yasujiro
Publication year - 2019
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.201806030
Subject(s) - regioselectivity , anthracene , chemistry , moiety , derivative (finance) , steric effects , adduct , supramolecular chemistry , molecule , molecular orbital , diels–alder reaction , population , photochemistry , stereochemistry , computational chemistry , organic chemistry , catalysis , demography , sociology , financial economics , economics
Abstract The regioselectivity in the Diels–Alder reaction of an unsymmetrical open‐cage C 60 derivative with anthracene was studied. By using an encapsulated H 2 molecule as a magnetic probe, the product population was successfully evaluated in detail, indicating the formation of approximately ten compounds as major components. The nucleus‐independent chemical shift (NICS) calculations showed a close resemblance to the observed 1 H NMR spectrum, which allowed for a facile characterization of the products. Theoretical studies on the formation of all 29 possible anthracene adducts were also performed. The results indicated that the regioselectivity is strongly governed by steric factors, values of the frontier orbital coefficients, and thermodynamic stabilities. Single‐crystal X‐ray analysis of the dominant compound revealed the supramolecular architecture between the anthracene moiety and the π‐sphere of a neighboring molecule.