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Volumn 121, Issue 18, 1999, Pages 4385-4396

Hydrogen/deuterium exchange reactions and transfer hydrogenations catalyzed by [C5Me5Rh(olefin)2] complexes: Conversion of alkoxysilanes to silyl enolates

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; DEUTERIUM; HYDROGEN; RHODIUM COMPLEX; SILANE DERIVATIVE; VINYL DERIVATIVE;

EID: 0033549039     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja984409o     Document Type: Article
Times cited : (98)

References (63)
  • 2
    • 0008813896 scopus 로고
    • Davies, J. A., Watson, P. L., Greenberg, A., Liebman, J. F., Eds.; VCH Publishers: New York
    • (a) Jones, W. D. In Selective Hydrocarbon Activation Principles and Progress; Davies, J. A., Watson, P. L., Greenberg, A., Liebman, J. F., Eds.; VCH Publishers: New York, 1990; p 113.
    • (1990) Selective Hydrocarbon Activation Principles and Progress , pp. 113
    • Jones, W.D.1
  • 37
    • 0000641250 scopus 로고
    • 2) by zinc reduction in methanol has been reported with moderate yields. Maitlis, P. M.; Kang, J. W. J. Organomet. Chem. 1970, 26, 393.
    • (1970) J. Organomet. Chem. , vol.26 , pp. 393
    • Maitlis, P.M.1    Kang, J.W.2
  • 38
    • 0007774570 scopus 로고
    • The coordination of vinyltrimethylsilane to a rhodium acetylacetonato system has been reported. Fitch, J. W.; Osterlih, W. T. J. Organomet. Chem. 1981, 213, 493.
    • (1981) J. Organomet. Chem. , vol.213 , pp. 493
    • Fitch, J.W.1    Osterlih, W.T.2
  • 39
    • 0010958984 scopus 로고
    • 2] complexes including the bis(vinyltrimethylsilane) complex. The formation of two isomers is observed in contrast to 1a, which shows essentially one isomer. Perutz, R. N.; Haddleton, D. M.; Duckett, S. B.; Belt, S. T. Organometallics 1989, 8, 748.
    • (1989) Organometallics , vol.8 , pp. 748
    • Perutz, R.N.1    Haddleton, D.M.2    Duckett, S.B.3    Belt, S.T.4
  • 46
    • 0344549914 scopus 로고    scopus 로고
    • note
    • 13C NMR analysis of these reaction mixtures shows a broad, ill-defined resonance at 0-2 ppm with extensive coupling to deuterium; for the olefin resonances see ref 33.
  • 47
    • 0345412131 scopus 로고    scopus 로고
    • note
    • 8) a triplet (1:1:1) resonance at 1.52 ppm (J = 1.8 Hz) is observed in addition to small amounts of unassigned decomposition products.
  • 48
    • 33947299181 scopus 로고
    • (a) An alternative mechanism for deuteration of the Cp* ligand follows a route via a fulvene rhodium hydride intermediate which operates under different conditions as applied in the reactions of 1a. Maitlis, P. M.; Moseley, K. J. Am. Chem. Soc. 1969, 91, 5970.
    • (1969) J. Am. Chem. Soc. , vol.91 , pp. 5970
    • Maitlis, P.M.1    Moseley, K.2
  • 49
    • 0344549912 scopus 로고    scopus 로고
    • note
    • 0 transition metal systems has been observed; see refs 1 and 2 for general references.
  • 50
    • 0344118265 scopus 로고    scopus 로고
    • note
    • 2 group; complex 1a decomposes after extensive deuteration to unassigned products. This result also indicates that protic mechanisms for H/D exchange catalyzed by possible decomposition products are not operative.
  • 51
    • 0344549907 scopus 로고    scopus 로고
    • note
    • 12 at 50°C results in the formation of new olefin complexes assigned as mono- and bis-cyclopentene rhodium species. Isolation of these materials was not successful.
  • 56
    • 0345412125 scopus 로고    scopus 로고
    • note
    • The doublet splitting of the β-protons disappears to generate a singlet for all four inequivalent positions, while the resonances for the α-protons are reduced to 30% in intensity at this stage.
  • 57
    • 0344549908 scopus 로고    scopus 로고
    • note
    • In the course of 2 h a second Cp*-containing species is generated which amounts to 21% of the rhodium complexes present relative to 1c. Additional olefin resonances suggest that this second species is an isomer of 1c. A fresh solution of crystallized 1c shows one isomer as indicated. Monitoring this solution over 1 week at 25°C shows that a second species with analogous NMR features as the complex indicated here is generated.
  • 58
    • 0345412123 scopus 로고    scopus 로고
    • note
    • Using n-propoxytrimethylsilane as substrate, reactions with norbornene, trimethylvinylsilane, or tert-butylethylene using 1a as a catalyst did not result in the formation of a silyl enolate and hydrogenation products.
  • 59
    • 0344118256 scopus 로고    scopus 로고
    • note
    • 3).
  • 60
    • 0344118260 scopus 로고    scopus 로고
    • note
    • A bis-olefin complex analogous to 1 using triphenylvinylsilane was prepared but not isolated without excess olefin present. This complex is more reactive in catalytic H/D exchange as discussed above due to the increased steric demand.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.