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Volumn 74, Issue 17, 2009, Pages 6442-6451

Examination of the mechanism of Rh2(II)-catalyzed carbazole formation using intramolecular competition experiments

Author keywords

[No Author keywords available]

Indexed keywords

BOND FORMATION; CHEMICAL EQUATIONS; ELECTROCYCLIZATION; ELECTRONIC DONATION; KINETIC ISOTOPE EFFECTS; PRODUCT RATIOS; STEREOSELECTIVE FORMATION;

EID: 69549086798     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo901224k     Document Type: Article
Times cited : (117)

References (188)
  • 86
    • 3242744539 scopus 로고
    • For reviews, see
    • For reviews, see: (a) Gassman, P. G. Acc. Chem. Res. 1970, 3, 26.
    • (1970) Acc. Chem. Res. , vol.3 , pp. 26
    • Gassman, P.G.1
  • 87
    • 0001901623 scopus 로고
    • Scriven, E. F. V., Ed.; Academic Press: Orlando
    • (b) Abramovitch, R. A.; Jeyaraman, R. In Azides and Nitrenes; Scriven, E. F. V., Ed.; Academic Press: Orlando, 1984; p 297.
    • (1984) Azides and Nitrenes , pp. 297
    • Abramovitch, R.A.1    Jeyaraman, R.2
  • 91
    • 3543085333 scopus 로고    scopus 로고
    • Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley-Interscience: Hoboken, NJ
    • (f) Falvey, D. E. In Reactive Intermediate Chemistry; Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley-Interscience: Hoboken, NJ, 2004; p 593.
    • (2004) Reactive Intermediate Chemistry , pp. 593
    • Falvey, D.E.1
  • 104
    • 33845374322 scopus 로고
    • For mechanistic and computational studes of Rh(II)-mediated carbene transfer reactions, see
    • For mechanistic and computational studes of Rh(II)-mediated carbene transfer reactions, see: (a) Taber, D. F.; Ruckle, R. E. J. Am. Chem. Soc. 1986, 108, 7686.
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 7686
    • Taber, D.F.1    Ruckle, R.E.2
  • 109
    • 69549091246 scopus 로고    scopus 로고
    • note
    • The rate-limiting step for Rh(II)-mediated decomposition of α-diazoesters is believed to be carbenoid generation; see ref 20.
  • 110
    • 0346362502 scopus 로고    scopus 로고
    • For recent examples of anilines employed as substrates in the Suzuki reaction, see
    • For recent examples of anilines employed as substrates in the Suzuki reaction, see: (a) Miura, Y.; Nishi, T.; Teki, Y. J. Org. Chem. 2003, 68, 10158.
    • (2003) Org. Chem. , vol.68 , pp. 10158
    • Miura, Y.1    Nishi, T.2    Teki, Y.J.3
  • 115
    • 0004024904 scopus 로고
    • The identity of an intramolecular isotope effect can enable insight into the mechanism of the product-determining step if it occurs after the rate-determining step. For a general discussion of the use of product isotope effects in mechanism determination, see: Wiley-Interscience: New York
    • The identity of an intramolecular isotope effect can enable insight into the mechanism of the product-determining step if it occurs after the rate-determining step. For a general discussion of the use of product isotope effects in mechanism determination, see: Carpenter, B. K., Determination of Organic Reaction Mechanisms; Wiley-Interscience: New York, 1984; pp 101-104.
    • (1984) Determination of Organic Reaction Mechanisms , pp. 101-104
    • Carpenter, B.K.1
  • 116
    • 0013035307 scopus 로고
    • For leading examples of the use of product isotope effect in mechanism determination, see
    • For leading examples of the use of product isotope effect in mechanism determination, see: (a) Dai, S.-H.; Dolbier, W. R. J. Am. Chem. Soc. 1972, 94, 3946.
    • (1972) J. Am. Chem. Soc. , vol.94 , pp. 3946
    • Dai, S.-H.1    Dolbier, W.R.2
  • 122
    • 0000705205 scopus 로고
    • For related isotope studies of C-H bond functionalization by rhodium carbenoids, see
    • For related isotope studies of C-H bond functionalization by rhodium carbenoids, see: (a) Wang, P.; Adams, J. J. Am. Chem. Soc. 1994, 116, 3296.
    • (1994) Am. Chem. Soc. , vol.116 , pp. 3296
    • Wang, P.1    Adams, J.J.2
  • 127
    • 69549128979 scopus 로고    scopus 로고
    • note
    • 5. This secondary kinetic isotope effect indicates that C-N bond formation and C-H bond cleavage are not concerted in the thermal reaction as well.
  • 128
    • 69549109516 scopus 로고    scopus 로고
    • note
    • A modest kinetic isotope effect (KIE = 1.9; cyclohexane solvent) was observed in the photolysis of 2-azidobiphenyl by Sundberg and co-workers (ref 13d). They imply that this result suggests that the singlet nitrene does not insert directly into the ortho-C-H bond but rather adds to the carbon.
  • 129
    • 0542443644 scopus 로고
    • For leading discussions of the correlation of the rate of the electrophilic aromatic substitution reaction with the Hammett equation, see
    • For leading discussions of the correlation of the rate of the electrophilic aromatic substitution reaction with the Hammett equation, see: (a) Jaffé, H. H. Chem. Rev. 1953, 53, 191.
    • (1953) Chem. Rev. , vol.53 , pp. 191
    • Jaffé, H.H.1
  • 136
    • 69549102619 scopus 로고    scopus 로고
    • note
    • For other Hammett correlation diagrams, see the Supporting Information.
  • 137
    • 69549134776 scopus 로고    scopus 로고
    • note
    • Caution should be exercised in drawing firm conclusions from the nonlinearity of the Hammett correlation using σ values for electrophilic reactions. Refer to ref 29 for a detailed discussion.
  • 142
    • 0001614570 scopus 로고
    • While 29 and 30 could interconvert, N-metalloimine isomerization would be slow in comparison to the subsequent C-N bond-forming step. Z/E thermal isomerization of imines was measured to be approximately 15-25 kcal/mol. See
    • While 29 and 30 could interconvert, N-metalloimine isomerization would be slow in comparison to the subsequent C-N bond-forming step. Z/E thermal isomerization of imines was measured to be approximately 15-25 kcal/mol. See: (a) Roberts, J. D.; Hall, G. E.; Middleton, W. J. J. Am. Chem. Soc. 1971, 93, 4778.
    • (1971) J. Am. Chem. Soc. , vol.93 , pp. 4778
    • Roberts, J.D.1    Hall, G.E.2    Middleton, W.J.3
  • 148
    • 69549112386 scopus 로고    scopus 로고
    • note
    • p values, the lines did not pass through the origin. See the Supporting Information or additional Hammett correlation plots.
  • 149
    • 0012422497 scopus 로고
    • U- or V-shaped Hammett plots have been interpreted as evidence for dual reaction mechanisms. For leading reports, see
    • U- or V-shaped Hammett plots have been interpreted as evidence for dual reaction mechanisms. For leading reports, see: (a) Fuchs, R.; Carlton, D. M. J. Am. Chem. Soc. 1963, 85, 104.
    • (1963) J. Am. Chem. Soc. , vol.85 , pp. 104
    • Fuchs, R.1    Carlton, D.M.2
  • 157
    • 69549105314 scopus 로고    scopus 로고
    • note
    • Smith and co-workers did not observe any linear correlation with Hammett substituent constants in the decomposition of 2-azidobiaryls. The reaction rate depended only on the arene bearing the azide group. See ref 11c.
  • 158
    • 69549119534 scopus 로고    scopus 로고
    • note
    • The error in slope and intercept was determined using least-squares analysis.
  • 159
    • 69549097153 scopus 로고    scopus 로고
    • note
    • When N-aryl-N-methylnitrenium ions were substituted with electron-donating groups, higher frequency aromatic C=C bond stretches were observed using time-resolved infared spectroscopy. Falvey and co-workers attributed the longer bond stretch to represent substantial charge delocalization in the aromatic system to favor a quinoid structure. See ref 17d.
  • 160
    • 14644411062 scopus 로고    scopus 로고
    • For recent reviews of 4π-electron-5-atom-electrocyclizations, see
    • For recent reviews of 4π-electron-5-atom-electrocyclizations, see: (a) Harmata, M. Chemtracts 2005, 17, 416.
    • (2005) Chemtracts , vol.17 , pp. 416
    • Harmata, M.1
  • 164
    • 69549125680 scopus 로고
    • Electrocyclization mechanisms have been suggested for the pyrolyses of 2-azidobenzophenones and 2-nitroazidobenzenes. For mechanistic studies, including Hammett correlations, see: (a) Patai, S., Rappoport, Z., Eds.; Wiley: New York, Chapter 7.
    • Electrocyclization mechanisms have been suggested for the pyrolyses of 2-azidobenzophenones and 2-nitroazidobenzenes. For mechanistic studies, including Hammett correlations, see: (a) Dyall, L. K. In The Chemistry of Functional Groups. Supplement D: The Chemistry of Halides, Pseudo-Halides, and Azides; Patai, S., Rappoport, Z., Eds.; Wiley: New York, 1968; Chapter 7.
    • (1968) The Chemistry of Functional Groups. Supplement D: the Chemistry of Halides, Pseudo-Halides, and Azides
    • Dyall, L.K.1
  • 167
    • 1642370535 scopus 로고    scopus 로고
    • A 6π-electron-5-atom electrocyclization was posited as a potential mechanism in the related deoxygenation of nitroaromatics; see
    • A 6π-electron-5-atom electrocyclization was posited as a potential mechanism in the related deoxygenation of nitroaromatics; see: (a) Davies, I. W.; Guner, V. A.; Houk, K. N. Org. Lett. 2004, 6, 743.
    • (2004) Org. Lett. , vol.6 , pp. 743
    • Davies, I.W.1    Guner, V.A.2    Houk, K.N.3
  • 170
    • 69549085880 scopus 로고    scopus 로고
    • note
    • In the related thermal nitrene C-H amination reaction, C-N bond formation is believed to precede N-H bond formation. See: (a) Reference .
  • 171
    • 0011330068 scopus 로고
    • Aryl and heteroaryl azides and nitrenes
    • Scriven, E. F. V., Ed.; Academic Press: London (mechanistic discussion pp 175-182)
    • (b) Smith, P. A. S. Aryl and heteroaryl azides and nitrenes. In Azides and Nitrenes, Reactivity and Utility; Scriven, E. F. V., Ed.; Academic Press: London, 1984; p 95 (mechanistic discussion pp 175-182).
    • (1984) Azides and Nitrenes, Reactivity and Utility , pp. 95
    • Smith, P.A.S.1
  • 172
    • 31944441649 scopus 로고    scopus 로고
    • A related diradical mechanism was proposed for the isomerization of aryl-substituted azirines to indoles; see
    • A related diradical mechanism was proposed for the isomerization of aryl-substituted azirines to indoles; see: Taber, D. F.; Tian, W. J. Am. Chem. Soc. 2006, 128, 1058.
    • (2006) Am. Chem. Soc. , vol.128 , pp. 1058
    • Taber, D.F.1    Tian, W.J.2
  • 173
    • 69549136645 scopus 로고    scopus 로고
    • note
    • 2-extrusion. We expect that the resulting nitrenoid to react faster with this ring than with the more electron-deficient ring, which is not necessarily in the plane.
  • 174
    • 84890760012 scopus 로고    scopus 로고
    • For discussions on the electronic nature of rhodium(II) nitrenoids, see: refs 5e, 14c, and: Evans, P. A., Ed.; Wiley: New York, (discussion on pp 402-405).
    • For discussions on the electronic nature of rhodium(II) nitrenoids, see: refs 5e, 14c, and: Espino, C. G.; Du Bois, J. In Modern Rhodium-Catalyzed Organic Reactions; Evans, P. A., Ed.; Wiley: New York, 2005; p 379 (discussion on pp 402-405).
    • (2005) Modern Rhodium-Catalyzed Organic Reactions , pp. 379
    • Espino, C.G.1    Du Bois, J.2
  • 175
    • 0000031028 scopus 로고
    • Some nucleophilic group 8 metal nitrenoid complexes have been reported. For leading examples, see: Ir
    • Some nucleophilic group 8 metal nitrenoid complexes have been reported. For leading examples, see: (a) Ir: Glueck, D. S.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1989, 111, 2719.
    • (1989) J. Am. Chem. Soc. , vol.111 , pp. 2719
    • Glueck, D.S.1    Hollander, F.J.2    Bergman, R.G.3
  • 179
    • 69549107148 scopus 로고    scopus 로고
    • note
    • b of singlet phenyl nitrene was measured to be -2 . See: (a) ref 18.
  • 181
    • 0034811817 scopus 로고    scopus 로고
    • For the use of dirhodium(II) complexes as Lewis acids, see
    • For the use of dirhodium(II) complexes as Lewis acids, see: (a) Doyle, M. P.; Phillips, I. M.; Hu, W. J. Am. Chem. Soc. 2001, 123, 5366.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 5366
    • Doyle, M.P.1    Phillips, I.M.2    Hu, W.3


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