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Volumn 121, Issue 28, 1999, Pages 6616-6623

Addition of olefins to aromatic ketones catalyzed by Rh(I) olefin complexes

Author keywords

[No Author keywords available]

Indexed keywords

ACETOPHENONE; ALKENE; AROMATIC HYDROCARBON; BENZOPHENONE DERIVATIVE; CYCLOPENTENE DERIVATIVE; KETONE; NORBORNENE DERIVATIVE; SILANE DERIVATIVE;

EID: 0033591902     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990702s     Document Type: Article
Times cited : (204)

References (72)
  • 2
    • 0008813896 scopus 로고
    • Davies, J. A., Watson, P. L., Greenberg, A., Liebman, J. F., Eds.; VCH Publishers: New York
    • 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
  • 25
    • 0345568807 scopus 로고    scopus 로고
    • note
    • 4 an ortho-metalated ruthenium hydride was isolated in which chelation of the carbonyl group to ruthenium was observed in the position trans to the hydride ligand, see ref 27.
  • 34
    • 0000360319 scopus 로고    scopus 로고
    • and references therein
    • Bosnich, B. Acc. Chem. Res. 1998, 31, 667 and references therein.
    • (1998) Acc. Chem. Res. , vol.31 , pp. 667
    • Bosnich, B.1
  • 40
    • 0000203047 scopus 로고
    • (a) Foo, T.; Bergman, R. G. Organometallics 1992, 11, 1801-1810. This example discusses Ir - indenyl complexes as a precursor for functionalization reactions.
    • (1992) Organometallics , vol.11 , pp. 1801-1810
    • Foo, T.1    Bergman, R.G.2
  • 46
    • 0344706694 scopus 로고    scopus 로고
    • note
    • The turnover frequency is 0.7 TO/h and compares well with the results for the reaction in cyclohexane.
  • 47
    • 0345137238 scopus 로고    scopus 로고
    • note
    • 8 followed by reversible H/D exchange are faster than productive aryl - alkyl coupling.
  • 48
    • 0344274771 scopus 로고    scopus 로고
    • note
    • Organic products have been isolated by chromatography and characterized by NMR spectroscopy and elemental analysis or HRMS; see Supporting Information.
  • 49
    • 0344274770 scopus 로고    scopus 로고
    • note
    • 1H NMR resonances for the methylene groups a to the aryl ring (3a, δ 2.65, 4a, δ 2.83; higher alkylation products, δ 3.11).
  • 50
    • 0345137235 scopus 로고    scopus 로고
    • note
    • The relatively high ratio of higher alkylated products suggests that the second alkylation might occur without prior release of the initially alkylated 2a. Also, the observation of secondary alkylation products in the deactivation process (vide infra) suggests this notion.
  • 51
    • 0345568802 scopus 로고    scopus 로고
    • note
    • Independent synthesis of a rhodium olefin complex with 3,3-dimethyl-1-butene was not successful. In situ NMR studies indicate the formation of such complexes as intermediates.
  • 52
    • 0344706692 scopus 로고    scopus 로고
    • note
    • It is curious to note that the ratio of endo to exo products in this reaction increases as the reaction proceeds with exo-3g being the exclusive addition product in the early stages of catalysis, which suggests that intermediates such as 5 or mixed olefin complexes generated from 1 and norbornene show different reactivity as the presumed bis-norbornene rhodium complex, which is assigned as the resting state during norbornene conversion.
  • 53
    • 0345137236 scopus 로고    scopus 로고
    • note
    • Analogous results are observed by Murai and co-workers using the Ru system in the reaction of 1-hexene (see refs 14-22).
  • 54
    • 0345137234 scopus 로고    scopus 로고
    • note
    • 2-); 7.95 (m, 2H, Ar); 7.04-7.18 (m, Ar.). MS/EI: 254.18.
  • 55
    • 0344274768 scopus 로고    scopus 로고
    • note
    • 3 protected enolate of acetophenone is commercially available.
  • 56
    • 0345568801 scopus 로고    scopus 로고
    • note
    • (b) A referee has suggested that formation of the silyl enolate might occur through a mechanism involving the addition of a rhodium hydride to the vinyl silane followed by β-silyl elimination and release of ethylene to generate a Rh - silyl complex. Insertion of ketone into the Rh -silyl bond followed by β-elimination would generate the silyl enolate and regenerate the rhodium hydride. While we cannot strictly rule out this mechanism, it is not apparent how a Rh - H species could be generated as the chain carrier in this system.
  • 57
    • 0345137232 scopus 로고    scopus 로고
    • note
    • 2); 1.96 (s, 3H, Me); 7.38 (s, 1H, Ar); 7.11 (d, 1H, Ar); 6.92 (d, 1H, Ar). MS/EI: 272.16.
  • 58
    • 0344274766 scopus 로고    scopus 로고
    • note
    • No site selectivity regarding the olefin was observed, which suggests that olefin insertion into a Rh hydride can occur with both regiochemistries under these conditions. This is especially remarkable since the exclusive products observed are based on anti-Markovnikov olefin addition. Olefinhydride insertion might be directed by the carbonyl group with respect to regiochemistry; no direct evidence for this is available.
  • 71
    • 0344274763 scopus 로고    scopus 로고
    • note
    • Labeling studies have shown that C - H bond activation is only observed in the ortho positions of acetophenone with use of the ruthenium catalyst; the other sites are not activated (see ref 16).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.