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Volumn 70, Issue 5, 2005, Pages 1630-1635

Dichlorocarbene addition to cyclopropenes: A computational study

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; BIFURCATION (MATHEMATICS); MATHEMATICAL MODELS; POTENTIAL ENERGY; REACTION KINETICS; SOLUTIONS;

EID: 84961983575     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo048161z     Document Type: Article
Times cited : (29)

References (55)
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    • Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York
    • Moss, R. A. In Carbenes; Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York, 1973; Vol. 1, pp 153-304.
    • (1973) Carbenes , vol.1 , pp. 153-304
    • Moss, R.A.1
  • 16
    • 84962343289 scopus 로고    scopus 로고
    • Brinker, U. H., Ed.; Elsevier: Amsterdam
    • For a review of carbene-alkene complexes, see: Merrer, D. C.; Moss, R. A. In Advances in Carbene Chemistry; Brinker, U. H., Ed.; Elsevier: Amsterdam, 2001; Vol. 3, pp 57-71.
    • (2001) Advances in Carbene Chemistry , vol.3 , pp. 57-71
    • Merrer, D.C.1    Moss, R.A.2
  • 21
    • 0346502730 scopus 로고    scopus 로고
    • Sevin, F.; McKee, M. L.; Shevlin, P. B. J. Org. Chem. 2004, 69, 382. This paper details reactions of carbenes with cyclopropane and more generally discusses reactions of carbenes with strained ring compounds to give new σ- and π-bonds simultaneously, as we observe here.
    • (2004) J. Org. Chem. , vol.69 , pp. 382
    • Sevin, F.1    McKee, M.L.2    Shevlin, P.B.3
  • 29
    • 2542495781 scopus 로고    scopus 로고
    • Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley: Hoboken, NJ
    • (a) Carpenter, B. K. In Reactive Intermediate Chemistry; Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley: Hoboken, NJ, 2004; pp 925-960.
    • (2004) Reactive Intermediate Chemistry , pp. 925-960
    • Carpenter, B.K.1
  • 31
    • 0037419851 scopus 로고    scopus 로고
    • Mechanistic bifurcations have been implicated in ene reactions of singlet oxygen (Singleton, D. A.; Hang, C.; Szymanski, M. J.; Meyer, M. P.; Leach, A. G.; Kuwata, K. T.; Chen, J. S.; Greer, A.; Foote, C. S.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 1319), bond shifting of cyclooctatetraene (Castaño, O.; Palmeiro, R.; Frutos, L. M.; Luisandrés, J. J. Comput. Chem. 2002, 23, 732), and the formation of a semi-bullvalene (Zhou, C.; Birney, D. M. Org. Lett. 2002, 4, 3279).
    • (2003) J. Am. Chem. Soc. , vol.125 , pp. 1319
    • Singleton, D.A.1    Hang, C.2    Szymanski, M.J.3    Meyer, M.P.4    Leach, A.G.5    Kuwata, K.T.6    Chen, J.S.7    Greer, A.8    Foote, C.S.9    Houk, K.N.10
  • 32
    • 0036572670 scopus 로고    scopus 로고
    • Mechanistic bifurcations have been implicated in ene reactions of singlet oxygen (Singleton, D. A.; Hang, C.; Szymanski, M. J.; Meyer, M. P.; Leach, A. G.; Kuwata, K. T.; Chen, J. S.; Greer, A.; Foote, C. S.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 1319), bond shifting of cyclooctatetraene (Castaño, O.; Palmeiro, R.; Frutos, L. M.; Luisandrés, J. J. Comput. Chem. 2002, 23, 732), and the formation of a semi-bullvalene (Zhou, C.; Birney, D. M. Org. Lett. 2002, 4, 3279).
    • (2002) J. Comput. Chem. , vol.23 , pp. 732
    • Castaño, O.1    Palmeiro, R.2    Frutos, L.M.3    Luisandrés, J.4
  • 33
    • 0037824494 scopus 로고    scopus 로고
    • Mechanistic bifurcations have been implicated in ene reactions of singlet oxygen (Singleton, D. A.; Hang, C.; Szymanski, M. J.; Meyer, M. P.; Leach, A. G.; Kuwata, K. T.; Chen, J. S.; Greer, A.; Foote, C. S.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 1319), bond shifting of cyclooctatetraene (Castaño, O.; Palmeiro, R.; Frutos, L. M.; Luisandrés, J. J. Comput. Chem. 2002, 23, 732), and the formation of a semi-bullvalene (Zhou, C.; Birney, D. M. Org. Lett. 2002, 4, 3279).
    • (2002) Org. Lett. , vol.4 , pp. 3279
    • Zhou, C.1    Birney, D.M.2
  • 40
    • 84962418890 scopus 로고    scopus 로고
    • note
    • The values for the transition states reported herein were determined via the quadratic synchronous transit method. Additionally, a similar structure was found for the 4a → 3a rearrangement, using an appropriate structure selected off the PES (Figure 4) as a starting point for the transition state calculations; this transition state was approximately 2.5 kcal/mol higher in energy than the one reported in the text.


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