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Volumn 27, Issue 4, 2008, Pages 602-608

Reaction of trans-Pd(styryl)Br(PMePh2)2 with styryl bromide affording 1,4-diphenyIbutadiene. An unexpected homocoupling process induced by P-C reductive elimination

Author keywords

[No Author keywords available]

Indexed keywords

ISOMERS; OLEFINS; REACTION KINETICS; SOLUTIONS; TOLUENE;

EID: 40549135332     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om701128e     Document Type: Article
Times cited : (19)

References (77)
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    • (a) de Meijere, A., Diederich, F., Eds. Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; Wiley-VCH: Weinheim, Germany, 2004.
    • (2004) Metal-Catalyzed Cross-Coupling Reactions
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    • For diene formation as a side reaction of cross-coupling, see: a
    • For diene formation as a side reaction of cross-coupling, see: (a) Negishi, E.; Takahashi, T.; Akiyoshi, K. J. Organomet. Chem. 1987, 334, 181-194.
    • (1987) J. Organomet. Chem , vol.334 , pp. 181-194
    • Negishi, E.1    Takahashi, T.2    Akiyoshi, K.3
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    • Yamamoto, A, Kurosawa, H, Eds, Elsevier: Amsterdam, Chapter 5
    • Osakada, K. In Current Methods in Inorganic Chemistry; Yamamoto, A., Kurosawa, H., Eds.; Elsevier: Amsterdam, 2003; Vol. 3,Chapter 5.
    • (2003) Current Methods in Inorganic Chemistry , vol.3
    • Osakada, K.1
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    • Ref 5a, Chapter 2
    • (b) Ref 5a, Chapter 2.
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    • P - C reductive elimination giving alkenylphosphonium complexes has been reported: (a) Rybin, L. V.; Petrovskaya, E. A.; Rubinskaya, M. I.; Kuz'mina, L. G.; Struchkov, Y. T.; Kaverin, V. V.; Koneva, N. Y. J. Organomet. Chem. 1985, 288, 119-129.
    • P - C reductive elimination giving alkenylphosphonium complexes has been reported: (a) Rybin, L. V.; Petrovskaya, E. A.; Rubinskaya, M. I.; Kuz'mina, L. G.; Struchkov, Y. T.; Kaverin, V. V.; Koneva, N. Y. J. Organomet. Chem. 1985, 288, 119-129.
  • 50
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    • 2 (4, ca. 2%), while most of (Z)-3 remained unreacted. GLC analysis revealed no formation of 1,4-diphenylbutadiene (2).
    • 2 (4, ca. 2%), while most of (Z)-3 remained unreacted. GLC analysis revealed no formation of 1,4-diphenylbutadiene (2).
  • 51
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    • 6 in the presence of (E)-1 (20 equiv).
    • 6 in the presence of (E)-1 (20 equiv).
  • 53
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    • 6 at 50 °C for 6 h.
    • 6 at 50 °C for 6 h.
  • 54
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    • Although 6 could not be isolated, it was assigned as [Pd(CH-CHPh)(μ- Br)(PMePh2)]2 based on the similarity of NMR data, 1H NMR: δ 2.14 (d, 2JHP, 11.4 Hz, PCH3, 31P(1H) NMR: δ 15.2 (s, to related [PdR(μ-Cl)(PMePh2)]2 R, Ph, CH 2Ph, Anderson, G. K. Organometallics 1983, 2, 665-668
    • 2Ph). Anderson, G. K. Organometallics 1983, 2, 665-668.
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    • The yield of 4 in each run of Figure 2(%): 94 (run 1), 96 (run 2), 98 (run 3).
    • (a) The yield of 4 in each run of Figure 2(%): 94 (run 1), 96 (run 2), 98 (run 3).
  • 56
    • 40549137862 scopus 로고    scopus 로고
    • The maximum amount of 5 derived from (E)-3 (%): 6 (run 1), 4 (run 2), 2 (run 3). Complex 5 was converted to 6 and 7 at the final stage as described for Figure 1.
    • (b) The maximum amount of 5 derived from (E)-3 (%): 6 (run 1), 4 (run 2), 2 (run 3). Complex 5 was converted to 6 and 7 at the final stage as described for Figure 1.
  • 57
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    • Aryl complexes undergo reversible P-C reductive elimination leading to intramolecular exchange of the PdAr1 and PAr2 groups: (a) Kong, K.-C, Cheng, C.-H. J. Am. Chem. Soc. 1991, 113, 6313-6315
    • 2 groups: (a) Kong, K.-C.; Cheng, C.-H. J. Am. Chem. Soc. 1991, 113, 6313-6315.
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    • T-shaped, three-coordinated complexes have been isolated for arylpalladium halides: (a) Stambuli, J. P.; Buhl, M.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 9346-9347.
    • T-shaped, three-coordinated complexes have been isolated for arylpalladium halides: (a) Stambuli, J. P.; Buhl, M.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 9346-9347.
  • 66
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    • Yamamoto, A, Kurosawa, H, Eds, Elsevier: Amsterdam, Chapter 9
    • (c) Ozawa, F. In Current Methods in Inorganic Chemistry; Yamamoto, A., Kurosawa, H., Eds.; Elsevier: Amsterdam, 2003; Vol. 3,Chapter 9.
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    • 2, the formation of A is possibly hindered by increasing coordination stability of the styrylphosphonium ligand.
    • 2, the formation of A is possibly hindered by increasing coordination stability of the styrylphosphonium ligand.


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