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Volumn 50, Issue 27, 2011, Pages 6128-6132

Palladium-catalyzed elimination/isomerization of enol triflates into 1,3-dienes

Author keywords

dienes; enol triflates; homogeneous catalysis; palladium; synthetic methods

Indexed keywords

1 ,3-DIENES; DIENES; ENOL TRIFLATES; HOMOGENEOUS CATALYSIS; HYDRIDE ELIMINATION; HYDROPALLADATION; REGIOSPECIFIC; SYNTHETIC METHODS;

EID: 79959516258     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201101820     Document Type: Article
Times cited : (45)

References (37)
  • 24
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    • Despite the prevailing notion that triflates are unstable and difficult to work with, our experiences with enol triflates derived from acetoacetates have been quite the contrary.
    • D. Babinski, O. Soltani, D. E. Frantz, Org. Lett. 2008, 10, 2901. Despite the prevailing notion that triflates are unstable and difficult to work with, our experiences with enol triflates derived from acetoacetates have been quite the contrary.
    • (2008) Org. Lett. , vol.10 , pp. 2901
    • Babinski, D.1    Soltani, O.2    Frantz, D.E.3
  • 25
    • 6044274630 scopus 로고    scopus 로고
    • 2] can be easily handled in air and weighed out on the benchtop, see
    • 2] can be easily handled in air and weighed out on the benchtop, see
    • (2004) J. Am. Chem. Soc. , vol.126 , pp. 13178
    • Hills, I.D.1    Fu, G.C.2
  • 27
    • 79959500842 scopus 로고    scopus 로고
    • 2] did not provide any of the diene product in comparable yield
    • 2] did not provide any of the diene product in comparable yield.
  • 29
    • 1242291816 scopus 로고    scopus 로고
    • We have yet to observe the intermediacy of the allene during the course of these reactions. Nonetheless, β-hydride eliminations from vinyl palladium(II) complexes to form allene intermediates have been proposed in other reactions although at much higher temperatures.
    • We have yet to observe the intermediacy of the allene during the course of these reactions. Nonetheless, β-hydride eliminations from vinyl palladium(II) complexes to form allene intermediates have been proposed in other reactions although at much higher temperatures., L. M. Lutete, I. Kadota, Y. Yamamoto, J. Am. Chem. Soc. 2004, 126, 1622.
    • (2004) J. Am. Chem. Soc. , vol.126 , pp. 1622
    • Lutete, L.M.1    Kadota, I.2    Yamamoto, Y.3
  • 32
    • 79959505121 scopus 로고    scopus 로고
    • An alternative explanation for the role of TMSOTf is the possibility that it promotes an unprecedented Z to E isomerization of the vinyl palladium(II) complex. In either case, however, the role of the carbonyl oxygen atom in attenuating reactivity remains the same
    • An alternative explanation for the role of TMSOTf is the possibility that it promotes an unprecedented Z to E isomerization of the vinyl palladium(II) complex. In either case, however, the role of the carbonyl oxygen atom in attenuating reactivity remains the same.
  • 33
    • 79959532523 scopus 로고    scopus 로고
    • In an effort to study the β-hydride elimination and hydropalladation steps more closely reactions with deuterium-labelled enol triflates were performed, but were inconclusive because of deuterium scrambling in the diene πsystem as a result of equilibrating Pd-H(D) intermediates. See the Supporting Information for more details
    • In an effort to study the β-hydride elimination and hydropalladation steps more closely reactions with deuterium-labelled enol triflates were performed, but were inconclusive because of deuterium scrambling in the diene πsystem as a result of equilibrating Pd-H(D) intermediates. See the Supporting Information for more details.
  • 34
    • 79959521832 scopus 로고    scopus 로고
    • The base-mediated elimination of triflic acid from enol triflates to provide the corresponding alkynoate (or allenoate) could serve as a potential pathway for these reactions that bypasses the initial oxidative addition and subsequent β-hydride elimination from a vinyl palladium(II) complex. The success of reactions in the absence of base, however, is evidence against this alternative pathway
    • The base-mediated elimination of triflic acid from enol triflates to provide the corresponding alkynoate (or allenoate) could serve as a potential pathway for these reactions that bypasses the initial oxidative addition and subsequent β-hydride elimination from a vinyl palladium(II) complex. The success of reactions in the absence of base, however, is evidence against this alternative pathway.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.