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Volumn 131, Issue 13, 2009, Pages 4584-4585

On the Pd-catalyzed vinylation of aryl halides with tris(alkoxy) vinylsilanes in water

Author keywords

[No Author keywords available]

Indexed keywords

ARYL HALIDES; DESILYLATION; HECK COUPLING; HIGH TEMPERATURE; NAOH SOLUTIONS; VINYL SILANE; VINYLATION;

EID: 67949104897     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja900333x     Document Type: Article
Times cited : (21)

References (24)
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    • For a stimulating discussion of the myths of (organo)catalysis in water, see: Blackmond, D. G.; Armstrong, A.; Coombe, V.; Wells, A. Angew. Chem., Int. Ed. 2007, 46, 3798-3800.
    • For a stimulating discussion of the "myths of (organo)catalysis in water", see: Blackmond, D. G.; Armstrong, A.; Coombe, V.; Wells, A. Angew. Chem., Int. Ed. 2007, 46, 3798-3800.
  • 5
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    • Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918-920. (b) Hatanaka, Y.; Fukushima, S.; Hiyama, T. Chem. Lett. 1989, 1711-1714.
    • (a) Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918-920. (b) Hatanaka, Y.; Fukushima, S.; Hiyama, T. Chem. Lett. 1989, 1711-1714.
  • 6
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    • 2nd ed, de Meijere, A, Diederich, F, Eds, Wiley-VCH: Weinheim, Germany, Chapter 4
    • (c) Denmark, S. E.; Sweis, R. F. In Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; de Meijere, A., Diederich, F., Eds.; Wiley-VCH: Weinheim, Germany, 2004; Chapter 4.
    • (2004) Metal-Catalyzed Cross-Coupling Reactions
    • Denmark, S.E.1    Sweis, R.F.2
  • 10
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    • Also see
    • (d) Shi, S.; Zhang, Y. J. Org. Chem. 2007, 72, 5927-5930. Also see:
    • (2007) J. Org. Chem , vol.72 , pp. 5927-5930
    • Shi, S.1    Zhang, Y.2
  • 16
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    • This pH value is essential for the observation of full conversions. The reaction can be activated with NaOH or with other bases such as sodium phosphate, whose Brönsted basicity is strong enough to attain pH >12
    • This pH value is essential for the observation of full conversions. The reaction can be activated with NaOH or with other bases such as sodium phosphate, whose Brönsted basicity is strong enough to attain pH >12.
  • 17
    • 85152999408 scopus 로고    scopus 로고
    • Formation of small amounts of [Si2O2(OH)3(vinyl)2]- and traces of other oligomers were also observed above pH 12. For studies on the alkaline hydrolysis of RSi(OR′3)3 species, see: Pozdniakova, Y. A.; Lyssenko, K. A.; Korlyukov, A. A.; Blagodatskikh, I. V.; Auner, N.; Katsoulis, D.; Shchegolikhina, O. I. Eur. J. Inorg. Chem. 2004, 1253-1261, and references therein.
    • Formation of small amounts of [Si2O2(OH)3(vinyl)2]- and traces of other oligomers were also observed above pH 12. For studies on the alkaline hydrolysis of RSi(OR′3)3 species, see: Pozdniakova, Y. A.; Lyssenko, K. A.; Korlyukov, A. A.; Blagodatskikh, I. V.; Auner, N.; Katsoulis, D.; Shchegolikhina, O. I. Eur. J. Inorg. Chem. 2004, 1253-1261, and references therein.
  • 18
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    • Silanolate 2 evolves to form water-insoluble species below pH 11.5-12. We are currently investigating whether the requirement of pH >12 is associated with the chemical nature or the water solubility of 2. Tetracoordinate silanolates have been introduced by Denmark and co-workers as activated substrates in Hiyama cross-coupling reactions. See: (a) Denmark, S. E, Baird, J. D. Chem.-Eur. J. 2006, 12, 4954-4963, and references therein
    • Silanolate 2 evolves to form water-insoluble species below pH 11.5-12. We are currently investigating whether the requirement of pH >12 is associated with the chemical nature or the water solubility of 2. Tetracoordinate silanolates have been introduced by Denmark and co-workers as activated substrates in Hiyama cross-coupling reactions. See: (a) Denmark, S. E.; Baird, J. D. Chem.-Eur. J. 2006, 12, 4954-4963, and references therein.
  • 20
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    • The competition between these routes in organic solvent has been studied in detail. See: Albe'niz, A. C.; Espinet, P.; Lo'pez-Ferna'ndez, R. Organometallics 2006, 25, 5449-5455. Also see: Kikukawa, K.; Ikenaga, K.; Kono, K.; Toritani, K.; Wada, F.; Matsuda, T. J. Organomet. Chem. 1984, 270, 277-282.
    • The competition between these routes in organic solvent has been studied in detail. See: Albe'niz, A. C.; Espinet, P.; Lo'pez-Ferna'ndez, R. Organometallics 2006, 25, 5449-5455. Also see: Kikukawa, K.; Ikenaga, K.; Kono, K.; Toritani, K.; Wada, F.; Matsuda, T. J. Organomet. Chem. 1984, 270, 277-282.
  • 22
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    • Related nucleophilic attacks by fluoride or hydroxide anions at the Si atom of a coordinated vinylsilane have been proposed for the Hiyama transmetalation step. For a recent reference, see: Sugiyama, A, Ohnishi, Y.-y, Nakaoka, M, Nakao, Y, Sato, H, Sakaki, S, Nakao, Y, Hiyama, T. J. Am. Chem. Soc. 2008, 130, 12975-12985
    • Related nucleophilic attacks by fluoride or hydroxide anions at the Si atom of a coordinated vinylsilane have been proposed for the Hiyama transmetalation step. For a recent reference, see: Sugiyama, A.; Ohnishi, Y.-y.; Nakaoka, M.; Nakao, Y.; Sato, H.; Sakaki, S.; Nakao, Y.; Hiyama, T. J. Am. Chem. Soc. 2008, 130, 12975-12985.
  • 23
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    • Hills, I. D.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 13178-13179. Also see: Lloyd-Jones, G. C.; Slatford, P. A. J. Am. Chem. Soc. 2004, 126, 2690- 2691.
    • Hills, I. D.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 13178-13179. Also see: Lloyd-Jones, G. C.; Slatford, P. A. J. Am. Chem. Soc. 2004, 126, 2690- 2691.
  • 24
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    • Under these ligand-free conditions, copious amounts of black Pd precipitation occur at the higher catalyst loadings needed for the observation of PdH resonances
    • Under these ligand-free conditions, copious amounts of black Pd precipitation occur at the higher catalyst loadings needed for the observation of PdH resonances.


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