Novel acid-catalyzed rearrangement of methanofullerenes bearing an α-ylidic ester to cyclopentanofullerenes: A vinyl cyclopropane-type ring expansion

Shih-Ching Chuang, Aminul Islam, Chih Wei Huang, Huai Ting Shih, Chien Hong Cheng*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

A novel acid-catalyzed ring expansion of methanofullerenes bearing an α-ylidic ester has been investigated. Treatment of dialkyl acetylenedicarboxylate and tricycloalkylphosphine with C60 led to the isolation of a methanofullerene ylide after passing the reaction mixtures through a basic alumina column. If the reaction mixture was passed through a silica gel column, a cyclopentanofullerene was isolated instead. These new cyclopentanofullerenes consisted of a fused cyclopentanone ring bearing an α-hydroxy ester and a phosphonium ylide and were confirmed by their NMR, mass, and X-ray diffraction data. The cyclopentanofullerenes were formed by the ring expansion of the corresponding methanofullerenes in the presence of silica gel. The ring expansion also proceeded by treating methanofullerene with acetic acid in chloroform. On the other hand, the methanofullerenes from RO2CCCCO2R, PAr3, and C60 were stable in silica gel. However, upon heating with acetic acid at 50 °C, they underwent ring expansion and dephosphination to give cyclopentenofullerenes. An implicit vinyl cyclopropane ring expansion mechanism was proposed to account for this novel acid-catalyzed rearrangement.

Original languageEnglish
Pages (from-to)3811-3816
Number of pages6
JournalJournal of Organic Chemistry
Volume68
Issue number10
DOIs
StatePublished - 1 May 2003

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