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Regioselective Cage Opening of La 2 @D 2 (10611)‐C 72 with 5,6‐Diphenyl‐3‐(2‐pyridyl)‐1,2,4‐triazine
Author(s) -
Yamada Michio,
Muto Yasuhiro,
Kurihara Hiroki,
Slanina Zdenek,
Suzuki Mitsuaki,
Maeda Yutaka,
Rubin Yves,
Olmstead Marilyn M.,
Balch Alan L.,
Nagase Shigeru,
Lu Xing,
Akasaka Takeshi
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201410012
Subject(s) - pentalene , chemistry , regioselectivity , intramolecular force , cycloaddition , cage , adamantane , crystallography , ring (chemistry) , derivative (finance) , triazine , aryne , single bond , stereochemistry , medicinal chemistry , molecule , catalysis , group (periodic table) , polymer chemistry , biochemistry , mathematics , organic chemistry , combinatorics , financial economics , economics
The thermal reaction of the endohedral metallofullerene La 2 @ D 2 (10611)‐C 72 , which contains two pentalene units at opposite ends of the cage, with 5,6‐diphenyl‐3‐(2‐pyridyl)‐1,2,4‐triazine proceeded selectively to afford only two bisfulleroid isomers. The molecular structure of one isomer was determined using single‐crystal X‐ray crystallography. The results suggest that the [4+2] cycloaddition was initiated in a highly regioselective manner at the CC bond connecting two pentagon rings of C 72 . Subsequent intramolecular electrocyclization followed by cycloreversion resulted in the formation of an open‐cage derivative having three seven‐membered ring orifices on the cage and a significantly elongated cage geometry. The reduction potentials of the open‐cage derivatives were similar to those of La 2 @ D 2 ‐C 72 whereas the oxidation potentials were shifted more negative than those of La 2 @ D 2 ‐C 72 . These results point out that further oxidation could occur easily in the derivatives.