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Cyclopenta[b]thienyl ligand in organometallic chemistry. Studies of the regioselectivity of the synthesis of new σ-element-substituted cyclopenta[b]thiophene derivatives

  • Organometallic Chemistry
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Abstract

Reactions of 2-ethyl-5-methylcyclopenta[b]thienyllithium (thiopentalenyllithium) (2) with various electrophilic reagents afford σ-element-substituted thiopentalenes. However, the reaction with Ph3SnCl yields only one of two possible isomers,viz, triphenyl(4H-cyclopenta[b] thiophen-4-yl)stannane (4c), whereas the reactions with Me3SiCl, Me3SiCl, or Ph2PCl give both possible isomers,viz., trimethyl(6H-cyclopenta[b]thiophen-6-yl)silane (3a) and trimethyl(4H-cyclopental[b]thiophen-4-yl)silane (4a), trimethyl(6H-cyclopenta[b]thiophen-6-yl)stannane (3b) and trimethyl(4H-cyclopental[b]thiophen-4-yl)stannane (4b), or diphenyl(6H-cyclopenta[b]thiophen-6-yl)phosphine (3d) and diphenyl(4H-cyclopenta[b]thiophen-4-yl)phosphine (4d) in ratios of 1∶2, 1∶2, or 1∶1, respectively. The structure of compound4c was established by X-ray diffraction analysis. The observed regioselectivity of formation of compound4c is attributed to the specific precoordination of the tin atom by the sulfur atom of the thiopentalenyl ligand and to the steric overcrowding of the Sn atom in organotin electrophiles.

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Vorob'evy Gory, 119899, Moscow, Russian Federation

    D. A. Kissounko, M. V. Zabalov, Yu. F. Oprunenko & D. A. Lemenovskii

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  1. D. A. Kissounko
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  2. M. V. Zabalov
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  3. Yu. F. Oprunenko
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  4. D. A. Lemenovskii
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Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1289, July, 2000.

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Kissounko, D.A., Zabalov, M.V., Oprunenko, Y.F. et al. Cyclopenta[b]thienyl ligand in organometallic chemistry. Studies of the regioselectivity of the synthesis of new σ-element-substituted cyclopenta[b]thiophene derivatives. Russ Chem Bull 49, 1282–1286 (2000). https://doi.org/10.1007/BF02495775

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  • DOI: https://doi.org/10.1007/BF02495775

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