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Highly Regioselective Synthesis of Bis‐Aziridino[60]fullerene with Sulfilimine
Author(s) -
Okada Mitsunori,
Nakahodo Tsukasa,
Ishitsuka Midori O.,
Nikawa Hidefumi,
Tsuchiya Takahiro,
Akasaka Takeshi,
Fujie Tetsuo,
Yoshimura Toshiaki,
Slanina Zdenek,
Nagase Shigeru
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201000244
Subject(s) - regioselectivity , electrophile , cycloaddition , chemistry , nitrene , nucleophile , fullerene , adduct , olefin fiber , medicinal chemistry , context (archaeology) , photochemistry , organic chemistry , catalysis , paleontology , biology
In the course of our study of the development of a synthetic methodology for the aziridination of fullerenes, we recently reported the photochemical [2+1] cycloaddition reaction of nitrene onto C 60 generated from sulfilimine. Sulfilimines with an electron‐donating group on the N atom are well known to undergo Michael‐type reactions, followed by concomitant elimination of sulfide to afford the corresponding aziridines. In these reactions, sulfilimines act as a nucleophile to the electrophilic olefins. Furthermore, C 60 has characteristic features of a low LUMO level and electron‐accepting properties. Therefore, it can be an electrophilic olefin. In this context, sulfilimines might react with C 60 to afford the corresponding aziridinofullerenes. We have studied the thermal reaction of ( S,S )‐diphenylsulfilimines with C 60 and regioselectively synthesized bis‐ and tris‐aziridinated fullerenes. These structures were determined through spectroscopic analyses. Among these, the structure of bis‐aziridinated[60]fullerene, C 60 (NCH 3 ) 2 , was determined using single‐crystal X‐ray analysis. Results show that the multi‐aziridination occurs exclusively at the same six‐membered ring of C 60 to afford one isomer of the bis‐adduct and tris‐adduct.