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Volumn 65, Issue 32, 2009, Pages 6354-6363

Chiral Lewis base promoted trichlorosilane reduction of ketimines. An enantioselective organocatalytic synthesis of chiral amines

Author keywords

Allyltrichlorosilane; Epoxide opening; Monoterpenes; Organocatalysis; Pyridine N oxides

Indexed keywords

AMINE; AMINOALCOHOL; HERBICIDE; IMINE; KETONE; LEWIS BASE; PICOLINIC ACID DERIVATIVE; SILANE DERIVATIVE;

EID: 67649620056     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2009.06.015     Document Type: Article
Times cited : (52)

References (56)
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    • and references cited therein. For a special issue on hydrogenation and transfer hydrogenation see:
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    • Reviews
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    • Reviews
    • Reviews:
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    • European Patent Application November 30, PCT/EP/2008/010079, November 27, 2008
    • Guizzetti, S.; Benaglia, M. European Patent Application November 30 2007; PCT/EP/2008/010079, November 27, 2008.
    • (2007)
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    • While we were proceeding with the European Patent application (see Ref. 14) and completing the experiments for submitting the present manuscript a communication was published:
    • While we were proceeding with the European Patent application (see Ref. 14) and completing the experiments for submitting the present manuscript a communication was published:. Zheng H., Deng J., Lin W., and Zhang X. Tetrahedron Lett. 48 (2007) 7934
    • (2007) Tetrahedron Lett. , vol.48 , pp. 7934
    • Zheng, H.1    Deng, J.2    Lin, W.3    Zhang, X.4
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    • note
    • For catalyst 1 several experiments of reduction reactions run at low temperature did not show any improvement in the stereoselection of the process.
  • 36
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    • For a discussion on the relative basicity of pyridine ring as function of the substituents see: The fact that 4 chloro picolinamide 29 behaved better than 4-methyl picolinamide 27 seems to suggest that electronic factors play a major role in fine tuning the catalytic activity and determining an optimum arrangement of the catalyst-trichlorosilane-imine adduct.
    • For a discussion on the relative basicity of pyridine ring as function of the substituents see: The fact that 4 chloro picolinamide 29 behaved better than 4-methyl picolinamide 27 seems to suggest that electronic factors play a major role in fine tuning the catalytic activity and determining an optimum arrangement of the catalyst-trichlorosilane-imine adduct. Brotzel F., Kempf B., Singer T., Zipse H., and Mayr H. Chem.-Eur. J. 13 (2007) 336
    • (2007) Chem.-Eur. J. , vol.13 , pp. 336
    • Brotzel, F.1    Kempf, B.2    Singer, T.3    Zipse, H.4    Mayr, H.5
  • 37
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    • note
    • Further details about the enantioselective reduction of aryl-alkyl ketones will be reported (manuscript in preparation).
  • 38
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    • note
    • Since in his report (Ref. 15) Zhang normally used catalyst 1 in 20 mol % amount, for sake of comparison we preferred to report in Table 5 the results obtained by us by employing both catalysts 1 and with 29 at 10%. In our hands catalyst 1 performed often better at 0 °C than at lower temperature.
  • 39
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    • European Patent Application. n.EP07023240.0, September 22, 2008
    • Guizzetti, S.; Benaglia, M. European Patent Application. n.EP07023240.0, September 22, 2008.
    • Guizzetti, S.1    Benaglia, M.2
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    • Enantioselective reductive amination: selected references for organometallic systems
    • Enantioselective reductive amination: selected references for organometallic systems:
  • 48
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    • note
    • Kocovsky has already described a one pot procedure which involves the in situ preparation of imine followed by trichlorosilane-mediated reduction (see Ref. 7d). With those formammide-based catalysts it was shown that the ketone reduction was slower than imine reduction. However with our catalytic systems only a fine tuning of the experimental conditions allowed to efficiently perform the reductive amination process.
  • 50
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    • For two recent contributions about the enantioselective synthesis of β-amino acids involving the use of trichlorosilane see
    • For two recent contributions about the enantioselective synthesis of β-amino acids involving the use of trichlorosilane see:


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.