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Volumn 10, Issue 14, 2008, Pages 2987-2989

Rh-catalyzed intermolecular cyclopropanation with α-alkyl-α- diazoesters: Catalyst-dependent chemo- and diastereoselectivity

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; AZO COMPOUND; ESTER; RHODIUM;

EID: 52049117459     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol800983y     Document Type: Article
Times cited : (51)

References (44)
  • 4
    • 52849093599 scopus 로고    scopus 로고
    • Karlin, K. A, Ed. Wiley: New York
    • (d) Doyle, M. P.; Ren, T. In Progress in Inorganic Chemistry; Karlin, K. A., Ed. Wiley: New York, 2001; Vol. 49, pp 113-168.
    • (2001) Progress in Inorganic Chemistry , vol.49 , pp. 113-168
    • Doyle, M.P.1    Ren, T.2
  • 10
    • 27544502534 scopus 로고    scopus 로고
    • Lowering temperature had been shown to have an effect on selectivity over β-hydride elimination in Rh2(S-PTTL)4- catalyzed, intramolecular C-H insertions: 99:1 selectivity was observed at -78°C vs 82:18 selectivity at 0°C. Minami, K, Saito, H, Tsutsui, H, Nambu, H, Anada, M, Hashimoto, S. Adv. Synth. Catal. 2005, 347, 1483
    • 4- catalyzed, intramolecular C-H insertions: 99:1 selectivity was observed at -78°C vs 82:18 selectivity at 0°C. Minami, K.; Saito, H.; Tsutsui, H.; Nambu, H.; Anada, M.; Hashimoto, S. Adv. Synth. Catal. 2005, 347, 1483.
  • 11
    • 0028272257 scopus 로고    scopus 로고
    • Modest improvements in selectivity over β-hydride elimination had been previously observed in intermolecular O-H insertions and intramolecular C-H insertions when sterically demanding ligands were used in room temperature. For an intermolecular O-H insertion reaction, 88:12 selectivity was observed with Rh2(1-adamantoate)4 vs 82:18 selectivity with Rh 2(OAc)4: (a) Cox, G. G, Haigh, D, Hindley, R. M, Miller, D. J, Moody, C. J. Tetrahedron Lett. 1994, 35, 3139
    • 4: (a) Cox, G. G.; Haigh, D.; Hindley, R. M.; Miller, D. J.; Moody, C. J. Tetrahedron Lett. 1994, 35, 3139.
  • 12
    • 2942567899 scopus 로고    scopus 로고
    • 4: (b) Taber, D. F.; Joshi, P. V. J. Org. Chem. 2004, 69, 4276.
    • 4: (b) Taber, D. F.; Joshi, P. V. J. Org. Chem. 2004, 69, 4276.
  • 20
    • 17044406664 scopus 로고    scopus 로고
    • Cu-catalyzed, intermolecular cyclopropanation reactions of alkenes with ethyl α-diazopropionate: (a) Gottschling, S. E.; Grant, T. N.; Milnes, K. K.; Jennings, M. C.; Baines, K. M. J. Org. Chem. 2005, 70, 2686.
    • Cu-catalyzed, intermolecular cyclopropanation reactions of alkenes with ethyl α-diazopropionate: (a) Gottschling, S. E.; Grant, T. N.; Milnes, K. K.; Jennings, M. C.; Baines, K. M. J. Org. Chem. 2005, 70, 2686.
  • 23
    • 0001238089 scopus 로고
    • For cyclopropanation reactions with ethyl α-diazopropionate via 1-pyrazolines, see: d
    • For cyclopropanation reactions with ethyl α-diazopropionate via 1-pyrazolines, see: (d) Doyle, M. P.; Dorow, R. L.; Tamblyn, W. H. J. Org. Chem. 1982, 47, 4059.
    • (1982) J. Org. Chem , vol.47 , pp. 4059
    • Doyle, M.P.1    Dorow, R.L.2    Tamblyn, W.H.3
  • 24
    • 0029164640 scopus 로고    scopus 로고
    • Intramolecular cyclopropanation reactions in the presence of β-hydrogens with Rh-catalysts, see ref 2 and: (a) Doyle, M. P, Zhou, Q.-L. Tetrahedron: Asymmetry 1995, 6, 2157
    • Intramolecular cyclopropanation reactions in the presence of β-hydrogens with Rh-catalysts, see ref 2 and: (a) Doyle, M. P.; Zhou, Q.-L. Tetrahedron: Asymmetry 1995, 6, 2157.
  • 31
    • 0025029270 scopus 로고    scopus 로고
    • With Cu catalysts: (h) Dauben, W. G, Hendricks, R. T, Luzzio, M. J, Ng, H. P. Tetrahedron Lett. 1990, 31, 6969
    • With Cu catalysts: (h) Dauben, W. G.; Hendricks, R. T.; Luzzio, M. J.; Ng, H. P. Tetrahedron Lett. 1990, 31, 6969.
  • 42
    • 59949093998 scopus 로고    scopus 로고
    • We know of several limitations of the Rh2TPA 4-catalyzed cyclopropanation reaction. Unlike the analogous reactions of ethyl α-diazopropionate to give 8f and 8g, the reactions of ethyl α-diazobutanoate (1 equiv) with either 1,1-diphenylethylene (3 equiv) or 1-vinylmesitylene (3 equiv) were both unsuccessful, and led predominantly to β-hydride elimination. Cyclopropane products were not observed in the reactions of ethyl α-diazobutanoate with 1-vinylcyclohexane, trans-β-methylstyrene, cis- diphenylethylene, or 1-octene. The reaction of ethyl α- diazohydrocinnamate (3 equiv) with styrene proceeded with poor efficiency: in hexane, the cyclopropanation product was formed in 28% yield (NMR analysis) along with uncharacterized products and unreacted styrene
    • 4-catalyzed cyclopropanation reaction. Unlike the analogous reactions of ethyl α-diazopropionate to give 8f and 8g, the reactions of ethyl α-diazobutanoate (1 equiv) with either 1,1-diphenylethylene (3 equiv) or 1-vinylmesitylene (3 equiv) were both unsuccessful, and led predominantly to β-hydride elimination. Cyclopropane products were not observed in the reactions of ethyl α-diazobutanoate with 1-vinylcyclohexane, trans-β-methylstyrene, cis- diphenylethylene, or 1-octene. The reaction of ethyl α- diazohydrocinnamate (3 equiv) with styrene proceeded with poor efficiency: in hexane, the cyclopropanation product was formed in 28% yield (NMR analysis) along with uncharacterized products and unreacted styrene.


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