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Volumn 23, Issue 6, 2004, Pages 1438-1447

Synthesis and Reactivity of Four-Membered Azapalladacycles Derived from N,N-Dialkyl-2-iodoanilines: Insertion Reactions of Carbenes into the Carbon-Palladium Bond

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; CARBON MONOXIDE; CATALYSIS; CHEMICAL BONDS; COMPLEXATION; MOLECULAR STRUCTURE; PALLADIUM; SOLUTIONS; SYNTHESIS (CHEMICAL); X RAY ANALYSIS;

EID: 1842533398     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om034270c     Document Type: Article
Times cited : (67)

References (68)
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    • 2, see: (a) Rodríguez-García, C.; Oliva, A.; Ortuño, R.-M.; Branchadell, V. J. Am. Chem. Soc. 2001, 123, 6157. (b) Straub, B. F. J. Am. Chem. Soc. 2002, 124, 14196. For the Pd-catalyzed dimerization of carbene ligands in group 6 metal-carbene complexes, see: (c) Sierra, M. A.; Mancheño, M. J.; Sáez, E.; del Amo, J. C. J. Am. Chem. Soc. 1998, 120, 6812. (d) Sierra, M. A.; del Amo, J. C.; Mancheño, M. J.; Gómez-Gallego, M. J. Am. Chem. Soc. 2001, 123, 851.
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    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 851
    • Sierra, M.A.1    Del Amo, J.C.2    Mancheño, M.J.3    Gómez-Gallego, M.4
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    • For other types of four-membered Pd-N-C-C palladacycles, see: (a) Arnek, R.; Zetterberg, K. Organometallics 1987, 6, 1230. (b) Falvello, L. R.; Forniés, J.; Navarro, R.; Sicilia, V.; Tomás, M. J. Chem. Soc., Dalton Trans. 1994, 3143. (c) Agnus, Y.; Gross, M.; Labarelle, M.; Louis, R.; Metz, B. J. Chem. Soc., Chem. Commun. 1994, 939. (d) Henderson, W.; Oliver, A. G.; Rickard, C. E. F.; Baker, L. J. Inorg. Chim. Acta 1999, 292, 260.
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    • For other types of four-membered Pd-N-C-C palladacycles, see: (a) Arnek, R.; Zetterberg, K. Organometallics 1987, 6, 1230. (b) Falvello, L. R.; Forniés, J.; Navarro, R.; Sicilia, V.; Tomás, M. J. Chem. Soc., Dalton Trans. 1994, 3143. (c) Agnus, Y.; Gross, M.; Labarelle, M.; Louis, R.; Metz, B. J. Chem. Soc., Chem. Commun. 1994, 939. (d) Henderson, W.; Oliver, A. G.; Rickard, C. E. F.; Baker, L. J. Inorg. Chim. Acta 1999, 292, 260.
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    • The oxidative addition of 2-iodoaniline to Pd(0) complexes has been described, see: (a) Vicente, J.; Abad, J.-A.; Frankland, A. D.; Ramírez de Arellano, M.-C. Chem. Commun. 1997, 959. (b) Vicente, J.; Abad, J.-A.; Frankland, A. D.; Ramírez de Arellano, M. C. Chem. Eur. J. 1999, 5, 3066.
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    • The oxidative addition of 2-iodoaniline to Pd(0) complexes has been described, see: (a) Vicente, J.; Abad, J.-A.; Frankland, A. D.; Ramírez de Arellano, M.-C. Chem. Commun. 1997, 959. (b) Vicente, J.; Abad, J.-A.; Frankland, A. D.; Ramírez de Arellano, M. C. Chem. Eur. J. 1999, 5, 3066.
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    • note
    • 12
  • 34
    • 1842441397 scopus 로고    scopus 로고
    • 2 means N,N-dimethyl-2-(diphenylphosphanyl)aniline
    • 2 means N,N-dimethyl-2-(diphenylphosphanyl)aniline.
  • 44
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    • note
    • For the insertion of carbon monoxide into the carbon-palladium bond of 2-aminophenylpalladium(II) complexes, see refs 14a,b.
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    • The existence of dichlorocarbene complexes of different transition metals has been unambiguously demonstrated, see for example: (a) Mansuy, D.; Lange, M.; Chottard, J. C.; Bartoli, J. F.; Chevrier, B.; Weiss, R. Angew. Chem., Int. Ed. Engl. 1978, 17, 781. (b) Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Am. Chem. Soc. 1980, 102, 1206.
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  • 47
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    • The existence of dichlorocarbene complexes of different transition metals has been unambiguously demonstrated, see for example: (a) Mansuy, D.; Lange, M.; Chottard, J. C.; Bartoli, J. F.; Chevrier, B.; Weiss, R. Angew. Chem., Int. Ed. Engl. 1978, 17, 781. (b) Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Am. Chem. Soc. 1980, 102, 1206.
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    • Clark, G.R.1    Marsden, K.2    Roper, W.R.3    Wright, L.J.4
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    • note
    • As the reaction mixtures were worked up in air, adventitious water could account for the hydrolysis process.
  • 49
    • 1842493591 scopus 로고    scopus 로고
    • note
    • However, if the hydrolysis had taken place, the migratory insertion from the resulting CO complex would be very favorable, from either a pentacoordinated CO complex or a square-planar CO complex with a cis arrangement between the aryl and the CO ligands.
  • 50
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    • 2 can be efficiently generated from chloroform and 50% NaOH. For a review on the generation of dichlorocarbene and its use in organic synthesis, see: Fedorynski, M. Chem. Rev. 2003, 103, 1099.
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    • Recently, a Pd(II) complex of a non-heteroatom-stabilized carbene ligand has been prepared by reaction of di(p-tolyl)diazomethane with Trpy-PdOAc, see: Bröring, M.; Brandt, C. D.; Stellwag, S. Chem. Commun. 2003, 2344.
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    • See also refs 3a and 3c
    • (b) See also refs 3a and 3c.
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    • note
    • 3, 200 MHz) δ 5.31 (d, J = 12.8 Hz, 1H), 4.48 (dd, J = 12.8 and 5.5 Hz, 1H), 3.54 (d, J = 2.8 Hz, 3H), 2.87 (d, J = 6.2 Hz, 1H).
  • 58
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    • See for example: (a) Sokolov, V. I.; Sorokina, T. A.; Troitskaya, L. L.; Solovieva, L. I.; Reutov, O. A. J. Organomet. Chem. 1972, 36, 389. (b) Yoneda, A.; Hakushi, T.; Newkome, G. R.; Fronczek, F. R. Organometallics 1994, 13, 4912. (c) Portscheller, J. L.; Malinakova, H. C. Org. Lett. 2002, 4, 3679, and references therein.
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    • Sokolov, V.I.1    Sorokina, T.A.2    Troitskaya, L.L.3    Solovieva, L.I.4    Reutov, O.A.5
  • 59
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    • See for example: (a) Sokolov, V. I.; Sorokina, T. A.; Troitskaya, L. L.; Solovieva, L. I.; Reutov, O. A. J. Organomet. Chem. 1972, 36, 389. (b) Yoneda, A.; Hakushi, T.; Newkome, G. R.; Fronczek, F. R. Organometallics 1994, 13, 4912. (c) Portscheller, J. L.; Malinakova, H. C. Org. Lett. 2002, 4, 3679, and references therein.
    • (1994) Organometallics , vol.13 , pp. 4912
    • Yoneda, A.1    Hakushi, T.2    Newkome, G.R.3    Fronczek, F.R.4
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    • and references therein
    • See for example: (a) Sokolov, V. I.; Sorokina, T. A.; Troitskaya, L. L.; Solovieva, L. I.; Reutov, O. A. J. Organomet. Chem. 1972, 36, 389. (b) Yoneda, A.; Hakushi, T.; Newkome, G. R.; Fronczek, F. R. Organometallics 1994, 13, 4912. (c) Portscheller, J. L.; Malinakova, H. C. Org. Lett. 2002, 4, 3679, and references therein.
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    • Portscheller, J.L.1    Malinakova, H.C.2
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    • note
    • As the reaction is carried out in the presence of an excess of, diazoalkane, the formation of disubstituted alkenes that could ba, inserted into the Pd-C bond of the four-membered palladacycle to give the six-membered palladacycle cannot be definitively ruled out.
  • 67
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    • note
    • PN(Me)Pr means N-methyl-N-propyl-2-(diphenylphosphanyl)-aniline.
  • 68
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    • computer program for the determination of crystal structure; University of Göttingen: Germany
    • Sheldrick, G. M. SHELXL97, computer program for the determination of crystal structure; University of Göttingen: Germany, 1997.
    • (1997) SHELXL97
    • Sheldrick, G.M.1


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