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Volumn 128, Issue 7, 2006, Pages 2452-2462

Experimental and computational studies on the mechanism of N-heterocycle C-H activation by Rh(I)

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; COMPUTATION THEORY; NITROGEN COMPOUNDS; RATE CONSTANTS;

EID: 33644502831     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0576684     Document Type: Article
Times cited : (181)

References (92)
  • 24
    • 2542641534 scopus 로고    scopus 로고
    • Some oxidative protocols for the heterocycle/olefin couple have appeared recently: (a) DeBoef, B.; Pastine, S. J.; Sames, D. J. Am. Chem. Soc. 2004, 126, 6556.
    • (2004) Am. Chem. Soc. , vol.126 , pp. 6556
    • DeBoef, B.1    Pastine, S.J.2    Sames, D.J.3
  • 40
    • 33644498947 scopus 로고    scopus 로고
    • note
    • While we have chosen to depict the metal center of 3 as square planar, we cannot rule out the presence of one weakly bound inner-sphere solvent ligand.
  • 42
    • 33644512867 scopus 로고    scopus 로고
    • Pre-agostic interactions have been identified as intermediates preceding C-H oxidative addition. The question of whether the C8-H bond of 3 can undergo metal-insertion is beyond the scope of this report. For a discussion of this rare type of interaction in a related system, see: Lewis, J. C.; Wu, J.; Bergman, R. G.; Ellman, J. A. Organometallics 2005, 24, 5737.
    • (2005) Organometallics , vol.24 , pp. 5737
    • Lewis, J.C.1    Wu, J.2    Bergman, R.G.3    Ellman, J.A.4
  • 47
    • 33644501579 scopus 로고    scopus 로고
    • note
    • 2H NMR.
  • 48
    • 33644526366 scopus 로고    scopus 로고
    • note
    • Another scenario that is consistent with the observed data is a large extent of crossover in conjunction with a large kinetic isotope effect. This interpretation is invalidated by the small measured kinetic isotope effect (vide infra).
  • 49
    • 33644541906 scopus 로고    scopus 로고
    • note
    • 3).
  • 52
    • 33644536516 scopus 로고    scopus 로고
    • note
    • 2RhCl, see ref 30a.
  • 53
    • 33644524188 scopus 로고    scopus 로고
    • note
    • 2RhCl.
  • 54
    • 33644552214 scopus 로고    scopus 로고
    • note
    • The omission of more complicated [Rh] equilibria was not found to affect data fitting.
  • 55
    • 33644524806 scopus 로고    scopus 로고
    • note
    • 3RhCl (ref 30b).
  • 60
    • 33644537470 scopus 로고    scopus 로고
    • note
    • For the sake of simplicity, no inner-sphere solvent molecules were included in our models. In a related system, reaction coordinates calculated with inner sphere solvent did not differ significantly from coordinates lacking solvation (ref 36a).
  • 62
    • 33644544841 scopus 로고    scopus 로고
    • note
    • 1H NMR resonances in the hydride region.
  • 63
    • 33644552884 scopus 로고    scopus 로고
    • note
    • 2RhCl (-10.4 cal/mol·K, ref 36a).
  • 64
  • 65
    • 33644499269 scopus 로고    scopus 로고
    • note
    • Maintaining N-coordination during C-H oxidative addition of an N-heterocycle would lead to a strained three-membered chelate ring. This type of coordination is known exclusively for early metals. See ref 8 and references therein.
  • 71
    • 33644516087 scopus 로고    scopus 로고
    • Reference 36b
    • (c) Reference 36b.
  • 74
    • 33644546136 scopus 로고    scopus 로고
    • note
    • We have once observed functionalization at such a site in the case of the purine (ref 15b).
  • 75
    • 2442591069 scopus 로고    scopus 로고
    • Efficient, versatile Rh-catalyzed hydroiminoacylation is possible when the imine N-substituent is a metal-coordinating group (2-pyridyl). See: Jun, C. H.; Lee, J. H. Pure Appl. Chem. 2004, 76, 577.
    • (2004) Pure Appl. Chem. , vol.76 , pp. 577
    • Jun, C.H.1    Lee, J.H.2
  • 84
    • 33644523194 scopus 로고    scopus 로고
    • note
    • Prepared according to the procedure for 4.
  • 89
    • 0007718740 scopus 로고    scopus 로고
    • Schrodinger, Inc.: Portland, OR
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.