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Volumn 130, Issue 42, 2008, Pages 13892-13899

Deeper insight into the mechanism of the reaction of photogenerated metallaketenes and imines

Author keywords

[No Author keywords available]

Indexed keywords

AMIDES; ATOMIC PHYSICS; ATOMS; CHROMIUM; CHROMIUM COMPOUNDS; NITROGEN COMPOUNDS; OXYGEN;

EID: 54249153780     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8024406     Document Type: Article
Times cited : (28)

References (54)
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    • Selected reviews in the chemistry and synthetic applications of Fischer carbene complexes: (a) Dötz, K. H.; Fischer, H.; Hofmann, P.; Kreissel, R.; Schubert, U.; Weiss, K. Transition Metal Carbene Complexes; Verlag Chemie: Deerfield Beach, FL, 1983.
    • Selected reviews in the chemistry and synthetic applications of Fischer carbene complexes: (a) Dötz, K. H.; Fischer, H.; Hofmann, P.; Kreissel, R.; Schubert, U.; Weiss, K. Transition Metal Carbene Complexes; Verlag Chemie: Deerfield Beach, FL, 1983.
  • 3
    • 0000533326 scopus 로고
    • Trost, B. M, Fleming, I, Eds, Pergamon: Oxford
    • (b) Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 5, p 1065.
    • (1991) Comprehensive Organic Synthesis , vol.5 , pp. 1065
    • Wulff, W.D.1
  • 4
    • 0000887836 scopus 로고
    • Abel, E. W, Stone, F. G. A, Wilkinson, G, Eds, Pergamon: Oxford
    • (c) Wulff, W. D. In Comprehensive Organometallic Chemistry 11; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol 12, p 470.
    • (1995) Comprehensive Organometallic Chemistry 11 , vol.12 , pp. 470
    • Wulff, W.D.1
  • 17
    • 0000951659 scopus 로고
    • Abel, E. W, Stone, F. G. A, Wilkinson, G, Eds, Pergamon: Oxford
    • (b) Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, p 549.
    • (1995) Comprehensive Organometallic Chemistry II , vol.12 , pp. 549
    • Hegedus, L.S.1
  • 20
    • 0000118303 scopus 로고    scopus 로고
    • and the earlier attempts to trap the photogenerated ketenes from irradiation of chromium(0)carbenes referenced therein
    • Gallager, M. L.; Greene, J. B.; Rooney, A. D. Organometallics 1997, 16, 5260 and the earlier attempts to trap the photogenerated ketenes from irradiation of chromium(0)carbenes referenced therein.
    • (1997) Organometallics , vol.16 , pp. 5260
    • Gallager, M.L.1    Greene, J.B.2    Rooney, A.D.3
  • 27
    • 54249127403 scopus 로고    scopus 로고
    • To ensure that all experiments were effected under identical conditions, two different sets of four samples each (one sample for each complex) for each solvent were irradiated at 15 cm of the light source in a irradiation chamber maintained to 25° by forced air circulation
    • To ensure that all experiments were effected under identical conditions, two different sets of four samples each (one sample for each complex) for each solvent were irradiated at 15 cm of the light source in a irradiation chamber maintained to 25° by forced air circulation.
  • 28
    • 54249120851 scopus 로고    scopus 로고
    • The effect of the solvent is, however, decisive in the carbonylation step as described in Figure 1. Coordinating solvents favor this step, while non-coordinating solvents hamper it. See ref 10 for a detailed discussion
    • The effect of the solvent is, however, decisive in the carbonylation step as described in Figure 1. Coordinating solvents favor this step, while non-coordinating solvents hamper it. See ref 10 for a detailed discussion.
  • 30
    • 0028109179 scopus 로고    scopus 로고
    • This enantio-discrimination observed in the conrotatory ring closure of the intermediate zwitterions in the formation of β-lactams is a case of asymmetric torquoselectivity. For a previous article in the asymmetric torquoselectivity of the Staudinger reaction, see: Cossío, F. P, Arrieta, A, Lecea, B, Ugalde, J. M. J. Am. Chem. Soc. 1994, 116, 2085
    • This enantio-discrimination observed in the conrotatory ring closure of the intermediate zwitterions in the formation of β-lactams is a case of asymmetric torquoselectivity. For a previous article in the asymmetric torquoselectivity of the Staudinger reaction, see: Cossío, F. P.; Arrieta, A.; Lecea, B.; Ugalde, J. M. J. Am. Chem. Soc. 1994, 116, 2085.
  • 36
    • 54249155570 scopus 로고    scopus 로고
    • Interestingly, all the efforts made (including solvent effects and different combinations of functionals/basis sets) to locate the corresponding TS's associated with the attack of imine 9 to 6b, were fruitless.
    • Interestingly, all the efforts made (including solvent effects and different combinations of functionals/basis sets) to locate the corresponding TS's associated with the attack of imine 9 to 6b, were fruitless.
  • 37
    • 54249153785 scopus 로고    scopus 로고
    • This situation contrasts with the thermally generated chromium(0)-and tungsten(0)ketene imines by the reaction with isonitriles. In this case, the reactive species toward nucleophiles are the corresponding metallacyclopropanoneimines and the 1,2-chiomatropic rearrangement from these complexes to N-metal coordinated ketenimines is strongly exothermic
    • (a) This situation contrasts with the thermally generated chromium(0)-and tungsten(0)ketene imines by the reaction with isonitriles. In this case, the reactive species toward nucleophiles are the corresponding metallacyclopropanoneimines and the 1,2-chiomatropic rearrangement from these complexes to N-metal coordinated ketenimines is strongly exothermic,
  • 41
    • 54249122595 scopus 로고    scopus 로고
    • Frisch, M. J. Gaussian 03, Revision C.02, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
    • Frisch, M. J. Gaussian 03, Revision C.02, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.