A Novel Ring Expansion of the Holey Ketolactam Derivative of C60

Iwamatsu, Sho‐ichi; Ono, Fumiaki; Murata, Shizuaki

doi:10.1246/cl.2003.614

Cited by 36 publications

(24 citation statements)

References 16 publications

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“…47 One methylene carbon was confirmed by both 1 H NMR and 13 C NMR spectra as described in the case of 11. In a similar way, the sequential cage scission reaction of 1 with ortho-phenylenediamine proceeded at 80 °C in the presence of an excess amount of pyridine to give 18a in 37% yield.…”

Section: Expansion Of the Orifice Of The Open-cage Ketolactam C 60mentioning

confidence: 70%

Open-Cage Fullerenes: Synthesis, Structure, and Molecular Encapsulation

Iwamatsu¹,

Murata²

2005

Synlett

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The carbon-carbon bond scission of the fullerene cage offers an open-cage fullerene derivative having an opening on the fullerene surface. This account summarizes our recent studies on the syntheses of open-cage C 60 derivatives as well as their properties of molecular encapsulation. The photochemical rearrangement of the cyclohexadiene derivative of C 60 gives bis(fulleroid), the precursor for the cage scission. The photooxygenative carbon-carbon bond cleavage of bis(fulleroid) affords an open-cage diketone derivative having a 12-membered ring. The reaction of the diketone derivative with aromatic hydrazine or hydrazone allows the ring expansion of the orifice by regioselective cage scission to yield a product bearing a 16-membered ring. The orifice in the product is large enough to pass a hydrogen molecule, producing an endohedral hydrogen complex. In the case of the reaction with ortho-phenylenediamine, two carbon-carbon bonds are sequentially cleaved to afford a product having a 20-membered ring orifice. This product spontaneously encapsulates one water molecule to form an endohedral water complex. Hydrogen (H 2 ) 4.2 Water 5Conclusion and Future Aspects

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Section: Expansion Of the Orifice Of The Open-cage Ketolactam C 60mentioning

confidence: 70%

Open-Cage Fullerenes: Synthesis, Structure, and Molecular Encapsulation

Iwamatsu¹,

Murata²

2005

Synlett

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“…[44] The reaction of amino-compounds with open-cage fullerene derivatives is an efficient method to form large holes capable of incorporating small molecules. [52] Iwamatsu and coworkers found that hydrazine or hydrazone or phenylenediamine reacted with the ketolactam 25 to form compounds 44 [53] and 45.…”

Section: Hole-enlargement Reactionsmentioning

confidence: 99%

Preparation of Open‐Cage Fullerenes and Incorporation of Small Molecules Through Their Orifices

Gan¹,

Yang²,

Zhang³

et al. 2010

Advanced Materials

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Open-cage fullerenes can act as hosts for small molecules such as water, nitrogen, or hydrogen, forming endohedral fullerenes. Following a brief summary of carbon, nitrogen, and oxygen insertion in the fullerene framework to form homofullerenes, methods of creating a hole in the fullerene surface are surveyed. Techniques of hole enlargement and the insertion of atoms or molecules through the orifice to form endohedral fullerenes are described. Finally, the possibility of subsequent closure of the hole is considered.

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“…The similar reaction was applied to ketolactam 20 by Iwamatsu and co-workers in 2003 [80] and tested by Orfanopoulos and co-workers in 2004 [81] (Scheme 9.32) to give a product with a 15-membered-ring orifice, whose structure was claimed to be 59 by the former and 60 by the latter. The difference in the structure between 59 and 60 arose from which of the two CbC double bonds, (a) or (b), was cleaved.…”

Section: Open-cage Fullerenes To Endohedral Fullerenes 403mentioning

confidence: 98%

“…The reaction of 51 with aromatic hydrazines gave 58 having a 16-membered-ring orifice in 50-89% yields (Scheme 9.31)[79].Scheme 9.28. Photooxygenative ring enlargement of 46.…”

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confidence: 99%