메뉴 건너뛰기




Volumn 130, Issue 40, 2008, Pages 13285-13293

Insights into directing group ability in palladium-catalyzed C-H bond functionalization

Author keywords

[No Author keywords available]

Indexed keywords

PALLADIUM; RATE CONSTANTS; REACTION KINETICS;

EID: 53549115668     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8045519     Document Type: Article
Times cited : (326)

References (90)
  • 11
    • 34547227201 scopus 로고    scopus 로고
    • For selected examples of palladium-catalyzed directed C-H activation/C-heteroatom bond-forming reactions, see: (a) Inamoto, K, Saito, T, Katsuno, M, Sakamoto, T, Hiroya, K. Org. Lett. 2007, 9, 2931
    • For selected examples of palladium-catalyzed directed C-H activation/C-heteroatom bond-forming reactions, see: (a) Inamoto, K.; Saito, T.; Katsuno, M.; Sakamoto, T.; Hiroya, K. Org. Lett. 2007, 9, 2931.
  • 21
    • 41449116165 scopus 로고    scopus 로고
    • For selected examples of palladium-catalyzed directed C-H activation/C-C bond-forming reactions, see: (a) Yu, W.-Y.; Sit, W. N.; Lai, K.-M.; Zhou, Z.; Chan, A. S. C. J. Am. Chem. Soc. 2008, 130, 3304.
    • For selected examples of palladium-catalyzed directed C-H activation/C-C bond-forming reactions, see: (a) Yu, W.-Y.; Sit, W. N.; Lai, K.-M.; Zhou, Z.; Chan, A. S. C. J. Am. Chem. Soc. 2008, 130, 3304.
  • 46
    • 36749082898 scopus 로고    scopus 로고
    • and references therein. For previous examples of the stoichiometric cyclopalladation of benzylpyridine, see: a
    • For previous examples of the stoichiometric cyclopalladation of benzylpyridine, see: (a) Mawo, R. Y.; Johnson, D. M.; Wood, J. L.; Smoliakova, I. P. J. Organomet. Chem. 2008, 693, 33, and references therein.
    • (2008) J. Organomet. Chem , vol.693 , pp. 33
    • Mawo, R.Y.1    Johnson, D.M.2    Wood, J.L.3    Smoliakova, I.P.4
  • 48
    • 53549116679 scopus 로고    scopus 로고
    • Notably, a similar strategy for electronically isolating an aryl ring from a directing group has been recently reported by Yu and co-workers in mechanistic studies of Pd-catalyzed oxazoline-directed arene oxygenation: Li, J. J.; Giri, R.; Yu, J. Q. Tetrahedron 2008, 64, 6987.
    • Notably, a similar strategy for electronically isolating an aryl ring from a directing group has been recently reported by Yu and co-workers in mechanistic studies of Pd-catalyzed oxazoline-directed arene oxygenation: Li, J. J.; Giri, R.; Yu, J. Q. Tetrahedron 2008, 64, 6987.
  • 50
    • 53549117946 scopus 로고    scopus 로고
    • See Supporting Information for full details of this calculation
    • See Supporting Information for full details of this calculation.
  • 51
    • 0029983984 scopus 로고    scopus 로고
    • a values used are in solution phase. (a) http://research.chem.psu.edu/brpgroup/pKa_compilation.pdf. (b) Borowiak-Resterna, A.; Szymanowski, J.; Voelkel, A. J. Radioanal. Nucl. Chem. Art. 1996, 208, 75-86.
    • a values used are in solution phase. (a) http://research.chem.psu.edu/brpgroup/pKa_compilation.pdf. (b) Borowiak-Resterna, A.; Szymanowski, J.; Voelkel, A. J. Radioanal. Nucl. Chem. Art. 1996, 208, 75-86.
  • 52
    • 53549126010 scopus 로고    scopus 로고
    • 2 = 0.80 in benzene) when these competition experiments were analyzed at low conversion (5-15% combined yield of the two products) as opposed to at the completion of the reaction.
    • 2 = 0.80 in benzene) when these competition experiments were analyzed at low conversion (5-15% combined yield of the two products) as opposed to at the completion of the reaction.
  • 53
    • 53549106561 scopus 로고    scopus 로고
    • Several oxazoline substrates were also examined, as these are widely used as directing groups for Pd-catalyzed C-H functionalization;2,3,6 however, these afforded uncatalyzed acetoxylation of the starting substrate. See ref 24 and the Supporting Information for full details
    • 2,3,6 however, these afforded uncatalyzed acetoxylation of the starting substrate. See ref 24 and the Supporting Information for full details.
  • 55
    • 0042728760 scopus 로고
    • and references therein
    • (b) Ryabov, A. D. Chem. Rev. 1990, 90, 403, and references therein.
    • (1990) Chem. Rev , vol.90 , pp. 403
    • Ryabov, A.D.1
  • 73
    • 53549087989 scopus 로고    scopus 로고
    • For examples of analogous electronic effects in reductive elimination from PdII, see: (a) Graham, D. C, Cavell, K. J, Yates, B. F. Dalton Trans. 2006, 1768
    • II, see: (a) Graham, D. C.; Cavell, K. J.; Yates, B. F. Dalton Trans. 2006, 1768.
  • 74
    • 53549109926 scopus 로고    scopus 로고
    • Nolan, S. P. In Palladium in Organic Synthesis; Tsuji, J., Ed. Topics in Organometallic Chemistry 14; Springer-Verlag: Berlin, Germany, 2005; pp 241-272.
    • (b) Nolan, S. P. In Palladium in Organic Synthesis; Tsuji, J., Ed. Topics in Organometallic Chemistry 14; Springer-Verlag: Berlin, Germany, 2005; pp 241-272.
  • 75
    • 53549124619 scopus 로고    scopus 로고
    • IV complexes with one alkyl/aryl ligand and three other X-type ligands: Alsters, P. L.; Engel, P. F.; Hogerheide, M. P.; Copijn, M.; Spek, A. L.; van Koten, G. Organometallics 1993, 12, 1831.
    • IV complexes with one alkyl/aryl ligand and three other X-type ligands: Alsters, P. L.; Engel, P. F.; Hogerheide, M. P.; Copijn, M.; Spek, A. L.; van Koten, G. Organometallics 1993, 12, 1831.
  • 76
    • 0000683856 scopus 로고    scopus 로고
    • IV complexes containing multiple σ-akyl and/or σ-aryl ligands have been isolated and shown to be stable at room temperature or above. (a) Markies, B. A.; Canty, A. J.; Boersma, J.; van Koten, G. Organometallics 1994, 13, 2053.
    • IV complexes containing multiple σ-akyl and/or σ-aryl ligands have been isolated and shown to be stable at room temperature or above. (a) Markies, B. A.; Canty, A. J.; Boersma, J.; van Koten, G. Organometallics 1994, 13, 2053.
  • 77
    • 53549135146 scopus 로고    scopus 로고
    • Byers, P. K, Canty, A. J, Skelton, B. W, White, A. H. Chem. Commun. 1986, 1722. However, the proposed intermediate in the current transformations is a monoaryl Pd species (B, Limited examples of such complexes have been observed, and all undergo rapid reductive elimination at room temperature see ref 20
    • (b) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. Chem. Commun. 1986, 1722. However, the proposed intermediate in the current transformations is a monoaryl Pd species (B). Limited examples of such complexes have been observed, and all undergo rapid reductive elimination at room temperature (see ref 20).
  • 78
    • 25144474992 scopus 로고    scopus 로고
    • We have reported that PdIV complexes containing two σ-aryl ligands can be stable at room temperature: Dick, A. R, Kampf, J. W, Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 12790
    • IV complexes containing two σ-aryl ligands can be stable at room temperature: Dick, A. R.; Kampf, J. W.; Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 12790.
  • 80
    • 53549133307 scopus 로고    scopus 로고
    • 2, 17b and 17c were still the major products, and <5% of the expected aromatic C-H functionalization product was formed. See Supporting Information for full details. (Chemical Equation Presented)
    • 2, 17b and 17c were still the major products, and <5% of the expected aromatic C-H functionalization product was formed. See Supporting Information for full details. (Chemical Equation Presented)
  • 89
    • 53549089261 scopus 로고    scopus 로고
    • 13a
    • 13a
  • 90
    • 53549084527 scopus 로고    scopus 로고
    • ‡) for the C-H activation step (the slow step of these transformations). See Supporting Information for further details.
    • ‡) for the C-H activation step (the slow step of these transformations). See Supporting Information for further details.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.