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Synthesis 2003(1): 0030-0034
DOI: 10.1055/s-2003-36245
PAPER
© Georg Thieme Verlag Stuttgart · New York

The First Generation of Azulenyl-Lithium and -Magnesium: A Novel, Versatile Method of Introducing a Substituent at the 2-Position of an Azulene Skeleton

Kei Kurotobia, Hiroshi Tabataa, Masato Miyauchia, Rahman A. F. M. Mustafizura, Kouto Migitaa, Toshihiro Murafuji*a, Yoshikazu Sugihara*a, Hirotsugu Shimoyamab, Kunihide Fujimori b
a Department of Chemistry, Faculty of Science, Yamaguchi University, Yamaguchi City 753-8512, Japan
Fax: +81(83)9335273; e-Mail: murafuji@po.cc.yamaguchi-u.ac.jp; e-Mail: sugihara@po.cc.yamaguchi-u.ac.jp;
b Department of Chemistry, Faculty of Science, Shinshu University, Asahi 3-1-1, Matsumoto 390-8621, Japan
Further Information

Publication History

Received 20 August 2002
Publication Date:
18 December 2002 (online)

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Abstract

1,3-Dihaloazulenes were effectively transformed into 2-substituted azulenes through lithiation at the 2-position by proton abstraction. Furthermore, 1,3-dichloro-2-iodoazulene was found to undergo iodine-lithium and -magnesium exchange to generate the corresponding azulenyl-lithium and -magnesium, respectively.

Key words

azulenes - lithium - magnesium - metalations - halogens

    References and Notes

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7

The single point energies of azulenyl anion and its biradical species were calculated by using the Gaussian 98 Revision A.6 program [8] at UHF/6-31G** level, based on the geometries optimized by semiempirical AM1 calculations.

9

The total energy of anion A was found to lie by about 11 kcal/mol above that of biradical B.