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Volumn 44, Issue 49, 2003, Pages 8777-8780

A highly selective photoinduced selenoperfluoroalkylation of terminal acetylenes by using a novel binary system of perfluoroalkyl iodide and diphenyl diselenide

Author keywords

Alkynes; Diselenide; High regioselectivity; High stereoselectivity; Perfluoroalkyl iodide; Photoinitiation; Radical reactions

Indexed keywords

ACETYLENE DERIVATIVE; FLUORINE DERIVATIVE; IODINE DERIVATIVE; SELENIDE; XENON;

EID: 0242329818     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2003.09.182     Document Type: Article
Times cited : (19)

References (43)
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    • For the introduction of both fluoroalkyl and phenylseleno groups into olefins by electroreduction, see: (a) Uneyama, K.; Yanagiguchi, T.; Asai, H. Tetrahedron Lett. 1997, 38, 7763; (b) Asai, H.; Uneyama, K. Chem. Lett. 1995, 1123; (c) Uneyama, K.; Kanai, M. Tetrahedron Lett. 1991, 32, 7425; (d) Uneyama, K.; Kitagawa, K. Tetrahedron Lett. 1991, 32, 3385.
    • (1997) Tetrahedron Lett. , vol.38 , pp. 7763
    • Uneyama, K.1    Yanagiguchi, T.2    Asai, H.3
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    • For the introduction of both fluoroalkyl and phenylseleno groups into olefins by electroreduction, see: (a) Uneyama, K.; Yanagiguchi, T.; Asai, H. Tetrahedron Lett. 1997, 38, 7763; (b) Asai, H.; Uneyama, K. Chem. Lett. 1995, 1123; (c) Uneyama, K.; Kanai, M. Tetrahedron Lett. 1991, 32, 7425; (d) Uneyama, K.; Kitagawa, K. Tetrahedron Lett. 1991, 32, 3385.
    • (1995) Chem. Lett. , pp. 1123
    • Asai, H.1    Uneyama, K.2
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    • For the introduction of both fluoroalkyl and phenylseleno groups into olefins by electroreduction, see: (a) Uneyama, K.; Yanagiguchi, T.; Asai, H. Tetrahedron Lett. 1997, 38, 7763; (b) Asai, H.; Uneyama, K. Chem. Lett. 1995, 1123; (c) Uneyama, K.; Kanai, M. Tetrahedron Lett. 1991, 32, 7425; (d) Uneyama, K.; Kitagawa, K. Tetrahedron Lett. 1991, 32, 3385.
    • (1991) Tetrahedron Lett. , vol.32 , pp. 7425
    • Uneyama, K.1    Kanai, M.2
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    • For the introduction of both fluoroalkyl and phenylseleno groups into olefins by electroreduction, see: (a) Uneyama, K.; Yanagiguchi, T.; Asai, H. Tetrahedron Lett. 1997, 38, 7763; (b) Asai, H.; Uneyama, K. Chem. Lett. 1995, 1123; (c) Uneyama, K.; Kanai, M. Tetrahedron Lett. 1991, 32, 7425; (d) Uneyama, K.; Kitagawa, K. Tetrahedron Lett. 1991, 32, 3385.
    • (1991) Tetrahedron Lett. , vol.32 , pp. 3385
    • Uneyama, K.1    Kitagawa, K.2
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    • f-I, giving the corresponding β-iodoallylic perfluoroalkanes regioselectively in good yields, see: Ogawa, A.; Imura, M.; Kamada, N.; Hirao, T. Tetrahedron Lett. 2001, 42, 2489.
    • (2001) Tetrahedron Lett. , vol.42 , pp. 2489
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    • f-I, and acetylenes in BTF homogeneous
    • f-I, and acetylenes in BTF homogeneous.
  • 33
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    • This selenoperfluoroalkylation can proceed in shorter reaction time: irradiation for 1.5 h resulted in the formation of 7a in 53% yield.
    • This selenoperfluoroalkylation can proceed in shorter reaction time: irradiation for 1.5 h resulted in the formation of 7a in 53% yield.
  • 34
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    • 2 adduct to acetylenes (8) was formed as a byproduct
    • 2 adduct to acetylenes (8) was formed as a byproduct.
  • 35
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    • Noteworthy is the excellent stereoselectivity of this selenoperfluoroalkylation. The bisselenation of acetylenes also proceeds, with high stereoselectivity in the initial stage, and however, E to Z isomerization takes place gradually and finally the reaction provides a stereoisomeric mixture based on the thermodynamical stability of both isomers
    • Noteworthy is the excellent stereoselectivity of this selenoperfluoroalkylation. The bisselenation of acetylenes also proceeds, with high stereoselectivity in the initial stage, and however, E to Z isomerization takes place gradually and finally the reaction provides a stereoisomeric mixture based on the thermodynamical stability of both isomers.
  • 36
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    • 21Se: 777.9690, found: 777.9686
    • 21Se: 777.9690, found: 777.9686.
  • 37
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    • It is also possible to purify the products by preparative TLC (or column chromatography) on silica gel (n-hexane)
    • It is also possible to purify the products by preparative TLC (or column chromatography) on silica gel (n-hexane).
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    • In general, vinylic radicals are believed to be a stereoisomeric mixture of σ-radicals, and a fast equilibrium is present between the stereoisomers, see:
    • In general, vinylic radicals are believed to be a stereoisomeric mixture of σ-radicals, and a fast equilibrium is present between the stereoisomers, see: Fessenden R.W., Schuler R.H. J. Chem. Phys. 39:1963;2147.
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    • The selenoperfluoroalkylation of ethyl propiolate requires long period of reaction time. Ethyl propiolate is assumed to generate vinylic π-radical, see: (a) Galli, C.; Guarnieri, A.; Koch, H.; Mencarelli, P.; Rappoport, Z. J. Org. Chem. 1997, 62, 4072; (b) Rubin, H.; Fischer, H. Helv. Chim. Acta 1996, 79, 1670; (c) Metzger, J. O.; Blumenstein, M. Chem. Ber. 1993, 126, 2493.
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    • The selenoperfluoroalkylation of ethyl propiolate requires long period of reaction time. Ethyl propiolate is assumed to generate vinylic π-radical, see: (a) Galli, C.; Guarnieri, A.; Koch, H.; Mencarelli, P.; Rappoport, Z. J. Org. Chem. 1997, 62, 4072; (b) Rubin, H.; Fischer, H. Helv. Chim. Acta 1996, 79, 1670; (c) Metzger, J. O.; Blumenstein, M. Chem. Ber. 1993, 126, 2493.
    • (1996) Helv. Chim. Acta , vol.79 , pp. 1670
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    • The selenoperfluoroalkylation of ethyl propiolate requires long period of reaction time. Ethyl propiolate is assumed to generate vinylic π-radical, see: (a) Galli, C.; Guarnieri, A.; Koch, H.; Mencarelli, P.; Rappoport, Z. J. Org. Chem. 1997, 62, 4072; (b) Rubin, H.; Fischer, H. Helv. Chim. Acta 1996, 79, 1670; (c) Metzger, J. O.; Blumenstein, M. Chem. Ber. 1993, 126, 2493.
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    • 2 was conducted, most of the starting trimethylsilylacetylene was also recovered
    • 2 was conducted, most of the starting trimethylsilylacetylene was also recovered.


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