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Volumn 9, Issue 20, 2007, Pages 3949-3952

Enantioselective iridium-catalyzed allylic amination of ammonia and convenient ammonia surrogates

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EID: 35048813934     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol701562p     Document Type: Article
Times cited : (116)

References (40)
  • 8
    • 0030940143 scopus 로고    scopus 로고
    • For work demonstrating branched selectivity with achiral ligands, see: f
    • For work demonstrating branched selectivity with achiral ligands, see: (f) Takeuchi, R.; Kashio, M. Angew. Chem., Int. Ed. 1997, 36, 263.
    • (1997) Angew. Chem., Int. Ed , vol.36 , pp. 263
    • Takeuchi, R.1    Kashio, M.2
  • 24
    • 0000276556 scopus 로고
    • Trost, B. M, Fleming, I, Eds, Pergamon: Oxford, UK
    • Godleski, S. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, UK, 1991; Vol. 4, p 585.
    • (1991) Comprehensive Organic Synthesis , vol.4 , pp. 585
    • Godleski, S.A.1
  • 28
    • 35048840884 scopus 로고    scopus 로고
    • For reactions of the neutral or anionic form of this nucleophile with two allylic carbonates, see refs 5 and 6
    • For reactions of the neutral or anionic form of this nucleophile with two allylic carbonates, see refs 5 and 6.
  • 33
    • 35048829002 scopus 로고    scopus 로고
    • Ring-closing metathesis of related materials after formation of the HBr salt has been reported to occur in good yield ref 6
    • Ring-closing metathesis of related materials after formation of the HBr salt has been reported to occur in good yield (ref 6).
  • 34
    • 84858344456 scopus 로고    scopus 로고
    • $0.78/g from Aldrich
    • $0.78/g from Aldrich.
  • 35
    • 35048817644 scopus 로고    scopus 로고
    • The linear monoallylation product could not be observed clearly in the 1H NMR spectrum, and could not be quantified. Thus, we do not report branched-to-linear selectivities for these reactions. Several signals corresponding to a majority of the mass balance were observed in the region of the 1H NMR spectrum in which the allylic hydrogens of linear products resonate, perhaps from formation of regioisomeric diallylation products. Nevertheless, these side products were easily removed from the branched product by flash chromatography, and good yields of the pure branched product were obtained. A larger excess of potassium trifluoroacetamide (2.4 equiv) increased the reaction rate and lowered the intensity of the resonances proposed to result from regioisomeric side products; however, it also increased the rate of decomposition of the carbonate to alcohol and did not measurably improve the overall yield
    • 1H NMR spectrum in which the allylic hydrogens of linear products resonate, perhaps from formation of regioisomeric diallylation products. Nevertheless, these side products were easily removed from the branched product by flash chromatography, and good yields of the pure branched product were obtained. A larger excess of potassium trifluoroacetamide (2.4 equiv) increased the reaction rate and lowered the intensity of the resonances proposed to result from regioisomeric side products; however, it also increased the rate of decomposition of the carbonate to alcohol and did not measurably improve the overall yield.


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