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Volumn 27, Issue 14, 2008, Pages 3378-3389

Associative transmetalation in the stille cross-coupling reaction to form dienes: Theoretical insights into the open pathway

Author keywords

[No Author keywords available]

Indexed keywords

PALLADIUM;

EID: 49349105775     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om701267r     Document Type: Article
Times cited : (40)

References (68)
  • 29
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    • For the reference for Gaussian03 see the Supporting Information.
    • For the reference for Gaussian03 see the Supporting Information.
  • 38
    • 49349115077 scopus 로고
    • - have been published: Lawrence, G. A
    • - have been published: Lawrence, G. A. Chem. Rev 1986, 86, 17.
    • (1986) Chem. Rev , vol.86 , pp. 17
  • 49
    • 49349099606 scopus 로고    scopus 로고
    • 3 (ref 15) is more favorable (on the order of 5 to 9 kcal/mol).
    • 3 (ref 15) is more favorable (on the order of 5 to 9 kcal/mol).
  • 50
    • 49349115561 scopus 로고    scopus 로고
    • + (VIII/IX).
    • + (VIII/IX).
  • 54
    • 49349111451 scopus 로고    scopus 로고
    • The pentacoordinated Pd species with trigonal-bipyramidal geometry initially proposed as transition state of the cyclic concerted process 14 could also be located only when the stannane, the vinyl, and the bromide ligands were placed on the equatorial plane of the bipyramid. Starting from the [Pd(PMe3)2(η2-vinylstannane, η1-vinyl)Br] intermediate XII with squarepyramidal geometry, transition structure TSXII-trans-VII was located, yielding the trans-square-planar complex trans-VII upon transmetalation. The overall activation barrier for the transmetalation via a cyclic five-coordinated mechanism was found to be considerably higher (56.1 kcal/mol in the gas phase from III · Br) than that corresponding to the formation of the cyclic four-coordinate mechanism previously characterized (36.0 kcal/mol in the gas phase).15 equation presente
    • 15 equation presented
  • 57
    • 33746191961 scopus 로고    scopus 로고
    • The same role for LiCl in Heck reactions of alkenyltosylates has been suggested (Hansen, A. L.; Ebran, J.-P.; Ahlquist, M.; Norrby, P.-O.; Skrydstrup, T. Angew. Chem., Int. Ed. 2006, 45, 3349).
    • The same role for LiCl in Heck reactions of alkenyltosylates has been suggested (Hansen, A. L.; Ebran, J.-P.; Ahlquist, M.; Norrby, P.-O.; Skrydstrup, T. Angew. Chem., Int. Ed. 2006, 45, 3349).
  • 60
    • 0041733970 scopus 로고    scopus 로고
    • For an X-ray structure of a pentacoordinate Pd(II) complex, see: Bröring, M.; Brandt, C. D. Chem. Commun. 2003, 2156.
    • For an X-ray structure of a pentacoordinate Pd(II) complex, see: Bröring, M.; Brandt, C. D. Chem. Commun. 2003, 2156.
  • 63
    • 18844392282 scopus 로고    scopus 로고
    • In a more recent study (Kozuch, S, Amatore, C, Jutand, A, Shaik, S. Organometallics 2005, 24, 2319),the relevance of the anionic intermediates in catalytic cycles was examined in the light of the energetic span (i.e, the energy difference between the summit and trough of the catalytic cycle, The trivalent anionic [Pd(PR3)2Cl, complex proved to be superior to the neutral one on substitution reactions with thiolates. A dual catalytic role was proposed, first stabilizing the transition state for oxidative addition, and second destabilizing the nucleophilic addition product using RS- as nucleophile. During oxidative addition, the chloride anion keeps a small P-Pd-P angle, a property of certain chelating diphosphines that has been found beneficial for the cross-coupling reactions of unreactive electrophiles. 49 The coordination of ArCl to the [Pd(PR3) 2Cl, speci
    • 45
  • 67
    • 33745930510 scopus 로고    scopus 로고
    • 52
    • 52


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.