Effective Synthesis of 1,3-Diselenole-2-selone-4,5-diselenolate (dsis) and its Utilization for the Synthesis of Selenocycle-fused Tetraselenafulvalene (TSF) Derivatives

Mie Kodani; Kazuo Takimiya; Yoshio Aso; Tetsuo Otsubo; Takashi Nakayashiki; Yoji Misaki

doi:10.1055/s-2001-16755

PAPER

Effective Synthesis of 1,3-Diselenole-2-selone-4,5-diselenolate (dsis) and its Utilization for the Synthesis of Selenocycle-fused Tetraselenafulvalene (TSF) Derivatives

Mie Kodani^a, Kazuo Takimiya*^a, Yoshio Aso^a, Tetsuo Otsubo*^a, Takashi Nakayashiki^b, Yoji Misaki^b
^a Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
Fax: +81(824)227191; e-Mail: ktakimi@hiroshima-u.ac.jp ;
^b Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan

Abstract

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Abstract

A facile and effective synthetic procedure for 1,3-diselenole-2-selone-4,5-diselenolate (dsis, 2) has been established. The utilization of 2 for the synthesis of selenocycle-fused tetraselenafulvalene derivatives is also reported.

Key words

lithiation - diselenolate ligands - protecting groups - ring-closure reaction - selenium-containing heterocycles

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References and Notes

<A NAME="RF03201SS-1">1</A> Svenstrup N. Becher J. Synthesis 1995, 215

For comprehensive reviews on organic superconductors, see:

<A NAME="RF03201SS-2A">2a</A> Williams JM. Ferraro JR. Thorn RJ. Carlson KD. Geiser U. Wang HH. Kini AM. Whangbo M.-H. Organic Superconductors (Including Fullerenes): Synthesis, Structure, Properties, and Theory Prentice Hall; New Jersey: 1992.

<A NAME="RF03201SS-2B">2b</A> Ishiguro T. Yamaji K. Saito G. Organic Superconductors 2nd ed.: Springer-Verlag; Berlin: 1998.

<A NAME="RF03201SS-3A">3a</A> Engler EM. Green DC. Chambers JQ. J. Chem. Soc., Chem. Commun. 1976, 148

<A NAME="RF03201SS-3B">3b</A> Olk R.-M. Dietzsch W. Hoyer E. Synth. React. Inorg. Met.-Org. Chem. 1984, 14: 915

<A NAME="RF03201SS-4">4</A> Matsubayashi G. Akiba K. Tanaka T. J. Chem. Soc., Dalton Trans. 1990, 115

<A NAME="RF03201SS-5">5</A> Steimecke G. Sieler H.-J. Kirmse R. Hoyer E. Phosphorus Sulfur 1979, 7: 49

<A NAME="RF03201SS-6">6</A> Wang C. Batsanov AS. Bryce MR. Howard JAK. Synthesis 1998, 1615

<A NAME="RF03201SS-7A">7a</A> Takimiya K. Morikami A. Otsubo T. Synlett 1997, 319

<A NAME="RF03201SS-7B">7b</A> Ogura F. Takimiya K. In Organoselenium Chemistry, A Practical Approach Back TG. Oxford University Press; New York: 1999. p.262-263

<A NAME="RF03201SS-8A">8a</A> Svenstrup N. Rasmussen KM. Hansen TK. Becher J. Synthesis 1994, 809

<A NAME="RF03201SS-8B">8b</A> Simonsen KB. Svenstrup N. Lau J. Simonsen O. Mørk P. Kristensen GJ. Becher J. Synthesis 1996, 407

(c) Essentially there should be no difference between cyanoethyl- and methoxycarbonylethyl- groups as a protecting group for thiolate or selenolate. However, in case of TSF selenolate derivatives, incorporation of cyanoethyl groups often leads to a serious decrease of solubility, making the subsequent deprotection/realkylation protocol difficult. Thus, we prefer the methoxycarbonylethyl group as a protecting group for the TSF selenolates.

Bis(ethylenediseleno)TSF (10) was synthesized in a low yield from 14 via corresponding ketone;

<A NAME="RF03201SS-10A">10a</A> Lee VY. Engler EM. Schumaker RR. Parkin SSP. J. Chem. Soc., Chem. Commun. 1983, 235

<A NAME="RF03201SS-10B">10b</A> Lee VY. Synth. Met. 1987, 20: 161