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Volumn 348, Issue 10-11, 2006, Pages 1289-1299

Asymmetric reductive amination: Convenient access to enantioenriched alkyl-alkyl or aryl-alkyl substituted α-chiral primary amines

Author keywords

Aliphatic amines; Asymmetric reductive amination; Chiral amines; Enantioenriched amines; Heterogeneous hydrogenation catalysts; Lewis acids; Titanium alkoxides

Indexed keywords


EID: 33746679902     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200606073     Document Type: Article
Times cited : (61)

References (99)
  • 4
    • 33746692267 scopus 로고    scopus 로고
    • note
    • The phrase chiral amine is loosely used, but generally refers to α-carbon stereocenters to nitrogen, for clarity we prefer to use the phrase α-chiral amine.
  • 13
    • 0000489118 scopus 로고    scopus 로고
    • [5] The enantioselective reduction of N-acetylenamides of unfunctionalized ketones (aryl alkyl ketones and pinacolone are the only viable substrates to date) has been extensively examined, but the non-acylated analogues are not viable substrates. Additionally, this strategy requires four reaction steps (aryl alkyl ketone to α-chiral primary amine) and is mediocre in overall yield, but delivers the product in exceptional high ee, see: a) M. J. Burk, G. Casy, N. B. Johnson, J. Org. Chem. 1998, 63, 6084-6085;
    • (1998) J. Org. Chem. , vol.63 , pp. 6084-6085
    • Burk, M.J.1    Casy, G.2    Johnson, N.B.3
  • 19
    • 29944440585 scopus 로고    scopus 로고
    • and references cited therein
    • c) A. Côté, A. B. Charette, J. Org. Chem. 2005, 70, 10864-10867, and references cited therein.
    • (2005) J. Org. Chem. , vol.70 , pp. 10864-10867
    • Côté, A.1    Charette, A.B.2
  • 26
    • 14844282688 scopus 로고    scopus 로고
    • Enantioselective reduction of C=N bonds and enamines with hydrogen
    • (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim
    • nd edn., (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim, 2004, pp. 113-123;
    • (2004) nd Edn. , pp. 113-123
    • Spindler, F.1    Blaser, H.-U.2
  • 31
    • 33746728006 scopus 로고    scopus 로고
    • note
    • [4b]
  • 42
    • 33746743463 scopus 로고    scopus 로고
    • (Avecia Limited, Great Britain), World Patent WO0112574, 2001
    • a) Transfer hydrogenation process: J. Martin, L. A. Campbell, (Avecia Limited, Great Britain), World Patent WO0112574, 2001;
    • Martin, J.1    Campbell, L.A.2
  • 43
    • 33746680956 scopus 로고    scopus 로고
    • (Avecia Limited, Great Britain). U. S. Patent 6,696,608, 2004
    • b) transfer hydrogenation process: J. Martin, L. A. Campbell, (Avecia Limited, Great Britain). U. S. Patent 6,696,608, 2004.
    • Martin, J.1    Campbell, L.A.2
  • 46
    • 33746698680 scopus 로고    scopus 로고
    • (Merial, France), U. S. Patent 6,562,953, 2003
    • c) a process which is useful for converting the carbonyl function in position 4″ of the cladinose unit of an aza-macrolide into an amine derivative: J. Dhainaut, P. Leon, F. Lhermitte, G. Oddon, (Merial, France), U. S. Patent 6,562,953, 2003.
    • Dhainaut, J.1    Leon, P.2    Lhermitte, F.3    Oddon, G.4
  • 51
    • 33746716546 scopus 로고    scopus 로고
    • (Degussa AG, Germany), U. S. Patent 6,884,887, 2005
    • e) method for producing amines by homogeneously catalyzed reductive amination of carbonyl compounds: T. Riermeier, K.-J. Haack, U. Dingerdissen, A. Boerner, V. Tararov, R. Kadyrov, (Degussa AG, Germany), U. S. Patent 6,884,887, 2005;
    • Riermeier, T.1    Haack, K.-J.2    Dingerdissen, U.3    Boerner, A.4    Tararov, V.5    Kadyrov, R.6
  • 54
    • 33746719057 scopus 로고    scopus 로고
    • [19a]
    • [19a]
  • 56
    • 0345276532 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2003, 42, 5472-5474;
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 5472-5474
  • 57
    • 33746704719 scopus 로고    scopus 로고
    • (Degussa AG, Germany). U. S. Patent 2004267051, 2004
    • b) method for the production of amines by reductive amination of carbonyl compounds under transfer-hydrogenation conditions: A. Börner, U. Dingerdissen, R. Kadyrov, T. Riermeier, V. Tararov, (Degussa AG, Germany). U. S. Patent 2004267051, 2004.
    • Börner, A.1    Dingerdissen, U.2    Kadyrov, R.3    Riermeier, T.4    Tararov, V.5
  • 59
    • 28044438742 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2005, 44, 7424-7427;
    • (2005) Angew. Chem. Int. Ed. , vol.44 , pp. 7424-7427
  • 61
    • 0011231534 scopus 로고
    • For examples of diastereoselective reduction of N-α-methylbenzyl ketimines, see: a) M. B. Eleveld, H. Hogeveen, E. P. Schudde, J. Org. Chem. 1986, 51, 3635-3642;
    • (1986) J. Org. Chem. , vol.51 , pp. 3635-3642
    • Eleveld, M.B.1    Hogeveen, H.2    Schudde, E.P.3
  • 66
    • 0002960798 scopus 로고    scopus 로고
    • For examples of dynamic kinetic diastereoselective reduction of α-alkoxy N-α-methylbenzylketimines, see: a) P. Bisel, E. Breitling, A. W. Frahm, Eur. J. Org. Chem. 1998, 729-733;
    • (1998) Eur. J. Org. Chem. , pp. 729-733
    • Bisel, P.1    Breitling, E.2    Frahm, A.W.3
  • 70
    • 33746686675 scopus 로고    scopus 로고
    • note
    • [5b] for an example using (R)- or (S)-phenylglycine amide (PGA).
  • 71
    • 0030914298 scopus 로고    scopus 로고
    • For an example of a dynamic kinetic diastereoselective reduction of a N-α-methylbenzylenanime of a β-keto ester, see: D. Xu, K. Prasad, O. Repič, T. J. Blacklock, Tetrahedron: Asymmetry 1997, 8, 1445-1451.
    • (1997) Tetrahedron: Asymmetry , vol.8 , pp. 1445-1451
    • Xu, D.1    Prasad, K.2    Repič, O.3    Blacklock, T.J.4
  • 84
    • 33746742054 scopus 로고    scopus 로고
    • note
    • [19a,][20a,b,d]
  • 85
    • 33746707248 scopus 로고    scopus 로고
    • note
    • Note that an examination of 3-octanone failed to provide a reasonable de (< 10%).
  • 86
    • 33746727389 scopus 로고    scopus 로고
    • note
    • [20f] for comparative data.
  • 87
    • 33746717218 scopus 로고    scopus 로고
    • note
    • Not examined were the following two possible solutions: 1) once the reductive amination reaction is complete, raise the hydrogen pressure to facilitate complete hydrogenolysis, or 2) for Raney-Ni or Pt-C ketones we never examined the possibility of completing the reductive amination reaction, and then simply adding Pd-C and continuing the hydrogenation to enable a one-pot (ketone to primary amine) reductive amination-hydrogenolysis sequence.
  • 88
    • 33746729521 scopus 로고    scopus 로고
    • Ontazolast: The evolution of a process
    • (Ed.: K. G. Gadamasetti), Marcel Dekker, New York
    • We recently became aware of Pd-C catalysts specifically for debenzylations and suppression of racemization, this may be helpful for this hydrogenolysis, see: V. Farina, K. Grozinger, H. Müller-Bötticher, G. P. Roth, Ontazolast: The Evolution of a Process, in: Process Chemistry in the Pharmaceutical Industry, (Ed.: K. G. Gadamasetti), Marcel Dekker, New York, 1999, pp. 107-124.
    • (1999) Process Chemistry in the Pharmaceutical Industry , pp. 107-124
    • Farina, V.1    Grozinger, K.2    Müller-Bötticher, H.3    Roth, G.P.4
  • 92
    • 0003780608 scopus 로고
    • (Ed.: M. T. Reetz), Springer-Verlag: Berlin, specifically see
    • b) M. T. Reetz, in: Organotitanium Reagents in Organic Synthesis, (Ed.: M. T. Reetz), Springer-Verlag: Berlin, 1986, specifically see p. 107.
    • (1986) Organotitanium Reagents in Organic Synthesis , pp. 107
    • Reetz, M.T.1
  • 98
    • 33746721824 scopus 로고    scopus 로고
    • [20g]
    • [20g]
  • 99
    • 33746688258 scopus 로고    scopus 로고
    • note
    • For example, for the use of chiral Lewis acid equivalents in combination with prochiral ketones and amines for enantioselective reductive amination, or as a starting point for the investigation of achiral Lewis acid derivatives thereof in the search for enhanced de and/or reaction rate with α-MBA or other amines.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.