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Volumn 129, Issue 28, 2007, Pages 8686-8687

Transition-state complexation in palladium-promoted [3,3] sigmatropic shifts

Author keywords

[No Author keywords available]

Indexed keywords

PALLADIUM;

EID: 34848917004     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja072159i     Document Type: Article
Times cited : (49)

References (31)
  • 9
    • 34848816462 scopus 로고    scopus 로고
    • Although intramolecular trapping of intermediates was described in ref 4b, substituted hexadienes and large ligands unlike any structure described herein were used. Our studies on how these factors affect the mechanism of the Pd(II)-promoted Cope rearrangement will be described in a future report
    • (c) Although intramolecular trapping of intermediates was described in ref 4b, substituted hexadienes and large ligands unlike any structure described herein were used. Our studies on how these factors affect the mechanism of the Pd(II)-promoted Cope rearrangement will be described in a future report.
  • 10
    • 0033601118 scopus 로고    scopus 로고
    • The Pd(0)-promoted Cope reaction is thought to proceed through a stepwise dissociative mechanism. See: Nakamura, H.; Iwama, H.; Ito, M.; Yamamoto, Y. J. Am. Chem. Soc. 1999, 121, 10850-10851. We will describe calculations on such reactions in a future report.
    • The Pd(0)-promoted Cope reaction is thought to proceed through a stepwise dissociative mechanism. See: Nakamura, H.; Iwama, H.; Ito, M.; Yamamoto, Y. J. Am. Chem. Soc. 1999, 121, 10850-10851. We will describe calculations on such reactions in a future report.
  • 11
    • 0006111078 scopus 로고    scopus 로고
    • In addition to aryl substitution at C2 of the diene, alkyl substitution at C1, C2, or C3, as well as phenyl or hydroxy substitution at C3 have all been experimentally explored. See, for example: Bluthe, N, Malacria, M, Gore, J. Tetrahedron Lett. 1983, 24, 1157-1160;
    • In addition to aryl substitution at C2 of the diene, alkyl substitution at C1, C2, or C3, as well as phenyl or hydroxy substitution at C3 have all been experimentally explored. See, for example: Bluthe, N.; Malacria, M.; Gore, J. Tetrahedron Lett. 1983, 24, 1157-1160;
  • 14
    • 34848926505 scopus 로고    scopus 로고
    • Calculations were performed at the B3LYP/LANL2DZ level of theory using Gaussian 03. Free energies at 25°C are reported throughout. See Supporting Information for additional details, including references and comparisons with other levels of theory (which suggest that the results described herein are not very sensitive to the level employed).
    • Calculations were performed at the B3LYP/LANL2DZ level of theory using Gaussian 03. Free energies at 25°C are reported throughout. See Supporting Information for additional details, including references and comparisons with other levels of theory (which suggest that the results described herein are not very sensitive to the level employed).
  • 15
    • 34848912508 scopus 로고    scopus 로고
    • 4a We will describe results that bear on this issue in a future report.
    • 4a We will describe results that bear on this issue in a future report.
  • 18
    • 34848915759 scopus 로고    scopus 로고
    • 3 (w/CPCM) resulted in a change of mechanism for both the R = H and R = CN cases from concerted to stepwise, but the well depths for these cases were only 0.1 and 1.1 kcal/mol, respectively. See Supporting Information for additional details.
    • 3 (w/CPCM) resulted in a change of mechanism for both the R = H and R = CN cases from concerted to stepwise, but the well depths for these cases were only 0.1 and 1.1 kcal/mol, respectively. See Supporting Information for additional details.
  • 19
    • 0038701495 scopus 로고    scopus 로고
    • This rearrangement can also be classified as a sigmahaptotropic rearrangement Goldschmidt, Z, Gottlier H. E, Cohen, D. J. Organomet. Chem. 1985, 294, 219-233, since the metal migrates over the allyl fragment to which it is attached as the Cope rearrangement occurs, ending up attached to the newly formed C=C π-bond
    • This rearrangement can also be classified as a " sigmahaptotropic" rearrangement (Goldschmidt, Z.; Gottlier H. E.; Cohen, D. J. Organomet. Chem. 1985, 294, 219-233), since the metal migrates over the allyl fragment to which it is attached as the Cope rearrangement occurs, ending up attached to the newly formed C=C π-bond.
  • 22
    • 33748225178 scopus 로고    scopus 로고
    • Complexation of Cope transition structures by Li+: Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1760-1763.
    • (b) Complexation of Cope transition structures by Li+: Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1760-1763.
  • 23
    • 34848922996 scopus 로고    scopus 로고
    • By halogens: Wang. S. C.; Tantillo, D. J. J. Phys. Chem. A, in press.
    • By halogens: Wang. S. C.; Tantillo, D. J. J. Phys. Chem. A, in press.
  • 24
    • 0347419941 scopus 로고    scopus 로고
    • Transition-state protonation: Hoffmann, R.; Tantillo, D. J. Angew. Chem., Int. Ed. 2003, 42, 5877-5882.
    • (c) "Transition-state protonation": Hoffmann, R.; Tantillo, D. J. Angew. Chem., Int. Ed. 2003, 42, 5877-5882.
  • 25
    • 33847801098 scopus 로고    scopus 로고
    • Seminal discussions of related concepts: Fukui, K.; Inagaki, S. J. Am. Chem. Soc. 1975, 97, 4445-4452.
    • (d) Seminal discussions of related concepts: Fukui, K.; Inagaki, S. J. Am. Chem. Soc. 1975, 97, 4445-4452.
  • 27
    • 34848888907 scopus 로고    scopus 로고
    • Note also that the Pd(II) version involves zwitterions rather than diradicals
    • Note also that the Pd(II) version involves zwitterions rather than diradicals.
  • 28
    • 33746321900 scopus 로고    scopus 로고
    • These intermediates should perhaps be described as para intermediates Northrop, B. H.; O'Malley, D. P.; Zografos, A. L.; Baran, P. S.; Houk, K. N. Angew. Chem., Int. Ed. 2006, 45, 4126-4130.
    • (a) These intermediates should perhaps be described as "para intermediates" (Northrop, B. H.; O'Malley, D. P.; Zografos, A. L.; Baran, P. S.; Houk, K. N. Angew. Chem., Int. Ed. 2006, 45, 4126-4130.
  • 30
    • 0034827199 scopus 로고    scopus 로고
    • and in some cases may reside on calderas (Doering, W. v. E.; Eklmanis, J. L.; Belfield, K. D.; Klärner, F. G.; Krawczyk, B. J. Am. Chem. Soc. 2001, 123, 5532-5541).
    • and in some cases may reside on "calderas" (Doering, W. v. E.; Eklmanis, J. L.; Belfield, K. D.; Klärner, F. G.; Krawczyk, B. J. Am. Chem. Soc. 2001, 123, 5532-5541).
  • 31
    • 34247531301 scopus 로고    scopus 로고
    • A recent paper describes, for some related [3,3] shifts of heterodienes, intermediates followed by small barriers to form the products: Watson, M. P.; Overman, L. E.; Bergman, R. G. J. Am. Chem. Soc. 2007, 129, 5031-5044.
    • (b) A recent paper describes, for some related [3,3] shifts of heterodienes, intermediates followed by small barriers to form the products: Watson, M. P.; Overman, L. E.; Bergman, R. G. J. Am. Chem. Soc. 2007, 129, 5031-5044.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.