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Volumn 64, Issue 3, 1999, Pages 698-699

Mild oxidative cleavage of borane-amine adducts from amide reductions: Efficient solution- and solid-phase synthesis of N-alkylamino acids and chiral oligoamines

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; BORANE DERIVATIVE;

EID: 0033525195     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo982290w     Document Type: Article
Times cited : (49)

References (38)
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    • For selected examples, see: (a) Gordon, D. W.; Steele, J. Bioorg. Med. Chem. Lett. 1995, 5, 47. (b) Matthews, J.; Rivero, R. A. J. Org. Chem. 1997, 62, 6090. (c) Bilodeau, M. T.; Cunningham, A. M. J. Org. Chem. 1998, 63, 2800. (d) Matthews, J.; Rivero, R. A. J. Org. Chem. 1998, 63, 4808.
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    • Gordon, D.W.1    Steele, J.2
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    • 0030876296 scopus 로고    scopus 로고
    • For selected examples, see: (a) Gordon, D. W.; Steele, J. Bioorg. Med. Chem. Lett. 1995, 5, 47. (b) Matthews, J.; Rivero, R. A. J. Org. Chem. 1997, 62, 6090. (c) Bilodeau, M. T.; Cunningham, A. M. J. Org. Chem. 1998, 63, 2800. (d) Matthews, J.; Rivero, R. A. J. Org. Chem. 1998, 63, 4808.
    • (1997) J. Org. Chem. , vol.62 , pp. 6090
    • Matthews, J.1    Rivero, R.A.2
  • 6
    • 0028833961 scopus 로고    scopus 로고
    • For selected examples, see: (a) Gordon, D. W.; Steele, J. Bioorg. Med. Chem. Lett. 1995, 5, 47. (b) Matthews, J.; Rivero, R. A. J. Org. Chem. 1997, 62, 6090. (c) Bilodeau, M. T.; Cunningham, A. M. J. Org. Chem. 1998, 63, 2800. (d) Matthews, J.; Rivero, R. A. J. Org. Chem. 1998, 63, 4808.
    • (1998) J. Org. Chem. , vol.63 , pp. 2800
    • Bilodeau, M.T.1    Cunningham, A.M.2
  • 7
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    • For selected examples, see: (a) Gordon, D. W.; Steele, J. Bioorg. Med. Chem. Lett. 1995, 5, 47. (b) Matthews, J.; Rivero, R. A. J. Org. Chem. 1997, 62, 6090. (c) Bilodeau, M. T.; Cunningham, A. M. J. Org. Chem. 1998, 63, 2800. (d) Matthews, J.; Rivero, R. A. J. Org. Chem. 1998, 63, 4808.
    • (1998) J. Org. Chem. , vol.63 , pp. 4808
    • Matthews, J.1    Rivero, R.A.2
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    • note
    • 5b of sulfonamide derivatives. The scope of these methods, however, was not demonstrated beyond N-methylation.
  • 19
    • 0031562077 scopus 로고    scopus 로고
    • For an example of a solid-phase synthesis of triamines from peptides on Merrifield resin, see: Nefzi, A.; Ostresh, J. M.; Meyer, J.-P.; Houghten, R. A. Tetrahedron Lett. 1997, 38, 931. Therein, acidic cleavage of borane-amine adducts is carried out with 1 M HCl/MeOH (65°C, >12 h). Also, with this support, product cleavage with HF requires special equipment.
    • (1997) Tetrahedron Lett. , vol.38 , pp. 931
    • Nefzi, A.1    Ostresh, J.M.2    Meyer, J.-P.3    Houghten, R.A.4
  • 23
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    • For examples of amide reductions, see: (a) Paikoff, S. J.; Wilson, T. E.; Cho, C. Y.; Schultz, P. G. Tetrahedron Lett. 1996, 37, 5653. (b) Brown, P. J.; Hurley, K. P.; Stuart, L. W.; Willson, T. M. Synthesis 1997, 778.
    • (1996) Tetrahedron Lett. , vol.37 , pp. 5653
    • Paikoff, S.J.1    Wilson, T.E.2    Cho, C.Y.3    Schultz, P.G.4
  • 24
    • 0030808173 scopus 로고    scopus 로고
    • For examples of amide reductions, see: (a) Paikoff, S. J.; Wilson, T. E.; Cho, C. Y.; Schultz, P. G. Tetrahedron Lett. 1996, 37, 5653. (b) Brown, P. J.; Hurley, K. P.; Stuart, L. W.; Willson, T. M. Synthesis 1997, 778.
    • (1997) Synthesis , pp. 778
    • Brown, P.J.1    Hurley, K.P.2    Stuart, L.W.3    Willson, T.M.4
  • 31
    • 0344107182 scopus 로고    scopus 로고
    • note
    • It was found that the reduction of unhindered N-acylamino acids such as 1a is accompanied by significant loss of material from the resin, presumably through reductive cleavage of the ester-based linker (ref 16) if more then 3 equiv of diborane is employed.
  • 33
    • 0344969680 scopus 로고    scopus 로고
    • note
    • 2 and dried under high vacuum for >12 h.
  • 34
    • 0344969678 scopus 로고    scopus 로고
    • note
    • Beads bearing the resulting borane-amine complex give a negative on the BPB test (yellow-green beads). A strong positive result (dark blue beads) is obtained following oxidative workup and neutralizing washes of the resin-bound secondary amine.
  • 35
    • 0344969679 scopus 로고    scopus 로고
    • note
    • 20 Column: Zorbax SB-C18 (4.6 × 150 mm, 5 mm). Eluent: linear gradient of 60-20% 0.1% aqueous TFA/acetonitrile over 20 min. Flow rate: 1 mL/ min. Analysis: UV diode-array detection, 190-400 nm.
  • 37
    • 0344538720 scopus 로고    scopus 로고
    • note
    • Conditions similar to those of ref 19 except for the eluent: 60-10% over 50 min.


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