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[3+2] Cycloaddition of Dialkyl ( E )‐Hex‐2‐en‐4‐ynedioates to [60]Fullerene by Phosphane‐Promoted Tandem α(δ′)‐Michael Additions
Author(s) -
Chuang ShihChing,
Deng JieCheng,
Chan FuWei,
Chen ShengYuan,
Huang WeiJe,
Lai LiHsiang,
Rajeshkumar Venkatachalam
Publication year - 2012
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201200024
Subject(s) - chemistry , cycloaddition , fullerene , fullerene chemistry , intramolecular force , nucleophile , homo/lumo , medicinal chemistry , tandem , nucleophilic addition , photochemistry , stereochemistry , organic chemistry , molecule , catalysis , materials science , composite material
Abstract Organophosphanes promote the [3+2] cycloaddition reactions of dialkyl ( E )‐hex‐2‐en‐4‐ynedioates and [60]fullerene, giving a series of cyclopenteno‐fullerenes 3a – k bearing phosphorus ylides. This cycloaddition reaction is initiated by the attack of nucleophilic phosphanes at the α(δ′)‐C atom of the dialkyl ( E )‐hex‐2‐en‐4‐ynedioate, which generates a 1,3‐dipolar species. These 1,3‐dipoles then react with C 60 followed by intramolecular cyclization to give cyclopenteno‐fullerenes in moderate‐to‐good yields. In a cyclic voltmmetry study, these novel fullerenes show a larger cathodic shift in their first reduction potential relative to [6,6]phenyl‐C 61 methyl butyrate, which indicates that these new derivatives possess higher LUMO energy levels.