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Volumn 120, Issue 28, 1998, Pages 6965-6979

Mechanistic and synthetic studies of the addition of alkyl aldehydes to vinylsilanes catalyzed by Co(I) complexes

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; COBALT;

EID: 0032558084     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja980610n     Document Type: Article
Times cited : (171)

References (98)
  • 36
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    • Jun, C-H.; Lee, H.; Hong, J.-B. J. Org. Chem. 1997, 62, 1200. Aminopyridines are used in this Rh catalyst system as cocatalysts for intermolecular hydroacylation.
    • (1997) J. Org. Chem. , vol.62 , pp. 1200
    • Jun, C.-H.1    Lee, H.2    Hong, J.-B.3
  • 38
    • 3543008554 scopus 로고    scopus 로고
    • note
    • 2] is more resistant toward ligand substitution.
  • 46
    • 3543012784 scopus 로고    scopus 로고
    • For complete structural data see the Supporting Information
    • For complete structural data see the Supporting Information.
  • 51
    • 3542999493 scopus 로고    scopus 로고
    • Unpublished results
    • 2], several isomers are observed in which the substituent on the olefin is directed either toward the other olefin substituent or toward the Cp* ligand. Brookhart, M.; Lenges, C. P. Unpublished results.
    • Brookhart, M.1    Lenges, C.P.2
  • 52
    • 3543004330 scopus 로고    scopus 로고
    • note
    • 3 resonance at -0.21; several olefinic resonances in the region of 2.5-0.3 ppm support this assignment.
  • 53
    • 3543017563 scopus 로고    scopus 로고
    • note
    • Addition of trimethylvinylsilane to a reaction mixture prepared in this fashion allows entry into a typical catalytic hydroacylation cycle and regeneration of the equilibrium mixture of 1 and 4.
  • 55
    • 3543031819 scopus 로고    scopus 로고
    • note
    • 1/2 ≃ 45 Hz) which corresponds to a Co-CO.
  • 56
    • 3543030660 scopus 로고    scopus 로고
    • note
    • 3] was not observed in this reaction, vide infra.
  • 59
    • 0000699784 scopus 로고
    • In comparison to other Co(III)-CO complexes the series of complexes of type 4 show relatively low CO bands. See for example: Dahl, L. F.; Nagaki, D. A.; Olson, W. L. Organometallics 1986, 5, 630-634.
    • (1986) Organometallics , vol.5 , pp. 630-634
    • Dahl, L.F.1    Nagaki, D.A.2    Olson, W.L.3
  • 60
    • 3543008553 scopus 로고    scopus 로고
    • note
    • 2] is observed.
  • 62
    • 3543046362 scopus 로고    scopus 로고
    • note
    • -1, 56 equiv.
  • 63
    • 3543043338 scopus 로고    scopus 로고
    • note
    • Kinetics are consistent with either rapid preequilibrium between 41 and 12 favoring 41 followed by reductive elimination or rate-determining trapping of 51 followed by rapid reductive elimination.
  • 64
    • 3543027649 scopus 로고    scopus 로고
    • note
    • 5).
  • 65
    • 3543018121 scopus 로고    scopus 로고
    • note
    • Repeated attempts to isolate 13 were not successful; decomposition to ketone 31 and unassigned organometallic products are observed.
  • 70
    • 0039650913 scopus 로고
    • In a subsequent study Bergman et al. investigated a similar Co(III)-metallacyclopentanone system. Even at high temperatures the formation of cyclobutanone was not observed. See: (a) Bergman, R. G.; Theopold, K. H. Organometallics 1982, 1, 1571-1579. (b) Bergman, R. G.; Theopold, K. H.; Becker, P. N. J. Am. Chem. Soc. 1982, 104, 5250-5252.
    • (1982) Organometallics , vol.1 , pp. 1571-1579
    • Bergman, R.G.1    Theopold, K.H.2
  • 71
    • 0037545891 scopus 로고
    • In a subsequent study Bergman et al. investigated a similar Co(III)-metallacyclopentanone system. Even at high temperatures the formation of cyclobutanone was not observed. See: (a) Bergman, R. G.; Theopold, K. H. Organometallics 1982, 1, 1571-1579. (b) Bergman, R. G.; Theopold, K. H.; Becker, P. N. J. Am. Chem. Soc. 1982, 104, 5250-5252.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 5250-5252
    • Bergman, R.G.1    Theopold, K.H.2    Becker, P.N.3
  • 74
    • 3543007362 scopus 로고    scopus 로고
    • note
    • 3); other products are not observed. During catalysis the formation of isomeric hexanals is observed as well.
  • 79
    • 3542994702 scopus 로고    scopus 로고
    • note
    • This reaction is observed with substrates without acidic α-protons to avoid competitive enolate-type transformations. The Tishenko analogue reaction reported here is curiously exclusive for alkyl aldehydes. Aromatic aldehydes show regular decarbonylation chemistry to 14 and 15 in the presence of excess aldehyde.
  • 80
    • 3543023518 scopus 로고    scopus 로고
    • note
    • Turnover numbers on the order of 50-100 are observed for aldehydes such as isobutyraldehyde or cyclohexanecarbaldehyde at 10 °C with turnover frequencies of ∼4 TO/h under these conditions. 4 persists to 90% conversion of aldehyde to ester; then deactivation is observed, and besides decarbonylation product 15 further unassigned organometallic complexes were observed.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.