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Synthesis 2008(23): 3749-3754  
DOI: 10.1055/s-0028-1083633
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Multilayered [3.3](3,5)Pyridinophanes [¹]

Masahiko Shibahara*a, Motonori Watanabeb, Kazuhiro Asoa, Teruo Shinmyozu*b
a Department of Chemistry, Faculty of Education and Welfare Science, Oita University, 700 Dannoharu, Oita 870-1192, Japan
Fax: +81(97)5547553; e-Mail: mshiba@cc.oita-u.ac.jp;
b Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, 6-10-1 Hakozaki, Fukuoka 812-8581, Japan
e-Mail: shinmyo@ms.ifoc.kyushu-u.ac.jp;
Further Information

Publication History

Received 2 July 2008
Publication Date:
06 November 2008 (online)

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Abstract

Two- to four-layered [3.3](3,5)pyridinophanes (PyPs) have been synthesized by the (4-tolylsulfonyl)methyl isocyanide (TosMIC) method. The coupling reaction between 3,5-bis[2-iso­cyano-2-(4-tolylsulfonyl)ethyl]pyridine (TosMIC adduct) and bis(chloromethyl) or tetrakis(bromomethyl) compounds in the presence of sodium hydride in N,N-dimethylformamide or sodium ­hydroxide and tetrabutylammonium iodide under high-dilution conditions gave the two-layered dione or three- and four-layered tetraones. Wolff-Kishner reduction of the ketones afforded the desired two- to four-layered [3.3](3,5)PyPs. The structure of the dione units take an anti geometry whereas the cyclophane units take a syn geometry­ in solution.

Key words

cyclophanes - pyridines - coupling reaction - ketones - Wolff-Kishner reduction

1

Multilayered [3.3]Cyclophanes, Part 4. For parts 1, 2, and 3, see refs. 12, 13a and 13b.

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1

Multilayered [3.3]Cyclophanes, Part 4. For parts 1, 2, and 3, see refs. 12, 13a and 13b.

10

Satou, T.; Sabae, M.; Iizuka, S.; Akita, M.; Shinmyozu, T. unpublished results.