環状 N, O-アセタールを利用するアルカロイド合成  [in Japanese] Alkaloid Synthesis Utilizing Cyclic N, O-Acetals  [in Japanese]

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Abstract

Synthesis and reaction of cyclic <I>N</I>, <I>O</I>-acetals can be of potential use and versatility in construction of polycyclic nitrogen heterocycles and alkaloid synthesis, as demonstrated in this review. The cyclic <I>N</I>-acyl-<I>N</I>, <I>O</I>-acetals, readily accessible by condensation of hydroxy-amines with ketocarboxylic acids, was transformed into the 2-azaspirocycles via intramolecular olefin-iminium cyclization mediated by TiCl<SUB>4</SUB>. Construction of the 6, 6-disubstituted 2-piperidone based on Lewis acid-mediated allylation of the cyclic <I>N</I>-acyl-<I>N</I>, <I>O</I>-acetals with allyltrimethylsilane led to a ladybird alkaloid adalinine in racemic form. This allylation reaction was performed with the cyclic <I>N</I>-acyl-<I>N</I>, <I>O</I>-acetal incorporating (<I>R</I>) -2- (1-aminoethyl) phenol as a chiral auxiliary to afford the (<I>R</I>) -6, 6-disubstituted 2-piperidone with high diastereoselectivity, which, on cleavage of the chiral auxiliary, provided (-) -adalinine. The enantioselective Lewis acid-mediated allylation of the cyclic <I>N</I>-acyl-<I>N</I>, <I>O</I>-acetals developed herein was successfully applied to the asymmetric syntheses of Dendrobatid alkaloids (-) -indolizidine 195B and 209D, and marine alkaloids (+) -stellettamide A and (-) -stellettamide B. On the other hand, intramolecular N, 0-acetalization of the keto-hydroxy-amines led to the one-step construction of the azabicyclononanes, which was then converted to the morphans. The azabicyclononane was subjected to bridgehead C-C bond formation with organometallic reagents via “anti-Bredt iminium ion” generated by treatment of aluminum reagents as Lewis acids. The 1-alkyl- and 1-vinylazabicyclononanes thus obtained were converted to the azatricyclododecane which is the core ring system of the novel immunosupressant FR 901483. The azabicyclononane formed by the <I>N</I>, <I>O</I>-acetalization of the keto-hydroxyamines was also elaborated into the diazatricyclododecane core of marine alkaloids madangamines.

Journal

  • Journal of Synthetic Organic Chemistry, Japan

    Journal of Synthetic Organic Chemistry, Japan 61(9), 868-881, 2003-09-01

    The Society of Synthetic Organic Chemistry, Japan

References:  54

  • <no title>

    GABBUTT C. D.

    Comprehensive Organic Functional Group Transformations 4, 293, 1995

    Cited by (1)

  • <no title>

    TAKAHASHI H.

    CHem.Pharm.Bull. 38, 2429, 1990

    Cited by (3)

  • <no title>

    ROMO D.

    Tetrahedron 47, 9503, 1991

    Cited by (1)

  • <no title>

    MEYERS A. I.

    J. Org. Chem. 56, 2294, 1991

    Cited by (1)

  • <no title>

    BURGESS L E.

    J. Am. Chem. Soc. 113, 9858, 1991

    Cited by (2)

  • <no title>

    YAMAMOTO Y.

    Synlett 1991, 339

    Cited by (1)

  • <no title>

    AMAT M.

    Tetrahedron Lett. 35, 2223, 1994

    Cited by (1)

  • <no title>

    YAMAZAKI N.

    Tetrahedron Lett. 37, 6161, 1996

    Cited by (2)

  • <no title>

    YAMAZAKI N.

    Tetrahedron Lett. 38, 4623, 1997

    Cited by (1)

  • <no title>

    COMINS D. L.

    J. Am. Chem. Soc. 115, 8851, 1993

    Cited by (1)

  • <no title>

    WILLIAMS D. R.

    Tetrahedron Lett. 39, 2675, 1998

    Cited by (2)

  • <no title>

    SCHOEMAKER H. E.

    Tetrahedron Lett. 1978, 1515

    Cited by (1)

  • <no title>

    SCHOEMAKER H. E.

    Tetrahedron 36, 951, 1980

    Cited by (2)

  • <no title>

    ZAUGG H. E.

    Synthesis 1984, 84, 181

    Cited by (2)

  • <no title>

    SPECKAMP W. N.

    Tetrahedron 41, 4367, 1985

    Cited by (1)

  • <no title>

    SPECKAMP W. N.

    Tetrahedron 56, 3817, 2000

    Cited by (1)

  • <no title>

    EVANS D. A.

    Tetrahedron Lett. 1979, 411

    Cited by (1)

  • <no title>

    EVANS D. A.

    J. Am. Chem. Soc. 104, 3695, 1982

    Cited by (1)

  • <no title>

    YAMAZAKI N.

    Synlett 1999, 37

    Cited by (1)

  • <no title>

    YAMAZAKI N.

    Tetrahedron Lett. 40, 739, 1999

    Cited by (1)

  • <no title>

    TRUSCH B.

    Tetrahedron Lett. 1973, 201

    Cited by (1)

  • <no title>

    LAURENT P.

    Tetrahedron 57, 3403, 2001

    Cited by (1)

  • <no title>

    YAMAZAKI N.

    Tetrahedron Lett. 42, 5029, 2001

    Cited by (2)

  • <no title>

    紺矢直人

    特開平 平 2-311446

    Cited by (1)

  • <no title>

    CHAPMAN D. T.

    Chem. Commun. 1996, 2415

    Cited by (1)

  • <no title>

    YAMAGUCHI T.

    Chem. Pharm. Bull. 46, 384, 1998

    Cited by (1)

  • <no title>

    ENDERS D.

    Tetrahedron: Asymmetry 8, 1895, 1997

    Cited by (8)

  • <no title>

    BLOCH R.

    Chem. Rev. 98, 1407, 1998

    Cited by (9)

  • <no title>

    CICCHI S.

    Tetrahedron Lett. 31, 3351, 1990

    Cited by (1)

  • <no title>

    JOHNSON F.

    Chem. Rev. 68, 375, 1968

    Cited by (4)

  • <no title>

    HOFFMANN R. W.

    Chem. Rev. 89, 1841, 1989

    Cited by (11)

  • <no title>

    ITOH T.

    Org. Lett. 4, 2469, 2002

    Cited by (1)

  • <no title>

    MYERS A. G.

    Tetrahedron Lett. 37, 3623, 1996

    Cited by (2)

  • <no title>

    YAMAZAKI N.

    Org. Lett. 2, 465, 2000

    Cited by (1)

  • <no title>

    DALY J. W.

    Alkaloids : Chemical and Biological Perspectives 4, ch.1, 1986

    Cited by (1)

  • <no title>

    DALY J. W.

    Fortschr. Chem. Org. Naturst. 41, 205, 1982

    Cited by (1)

  • <no title>

    ARONSTAM R. S.

    Neurochem. Res. 11, 1227, 1986

    Cited by (1)

  • <no title>

    YAMAZAKI N.

    Org. Lett. 3, 193, 2001

    Cited by (1)

  • <no title>

    HIROTA H.

    Tetrahedron Lett. 31, 4163, 1990

    Cited by (1)

  • <no title>

    ABE Y.

    Br. J. Pharmacol. 121, 1309, 1997

    Cited by (1)

  • <no title>

    WHITLOCK G. A.

    J. Org. Chem. 62, 7916, 1997

    Cited by (1)

  • <no title>

    WHITLOCK G. A.

    Helv. Chim. Acta. 83, 2007, 2000

    Cited by (1)

  • <no title>

    SHIN J.

    J. Nat. Prod. 60, 611, 1997

    Cited by (1)

  • <no title>

    MORLEY C.

    Tetrahedron : Asymmetry 1, 147, 1990

    Cited by (1)

  • <no title>

    YAMAZAKI N.

    J. Org. Chem. 62, 8280, 1997

    Cited by (1)

  • <no title>

    TODA M.

    Tetrahedron Lett. 1972, 335

    Cited by (1)

  • <no title>

    SASAKI T.

    J. Am. Chem. Soc. 105, 5912, 1983

    Cited by (1)

  • <no title>

    SUZUKI H.

    Tetrahedron Lett. 42, 3013, 2001

    Cited by (1)

  • <no title>

    SAKAMOTO K.

    J. Antibiot 49, 37, 1996

    Cited by (1)

  • <no title>

    KONG F.

    J. Am. Chem. Soc. 116, 6007, 1994

    Cited by (3)

  • <no title>

    HIKAGE N.

    Tetrahedron Lett. 39, 6237, 1998

    DOI  Cited by (4)

  • <no title>

    ITO T.

    Synlett 2001, 1506

    DOI  Cited by (1)

  • <no title>

    LOGNAY G.

    J. Nat. Prod. 59, 510, 1996

    DOI  Cited by (1)

  • <no title>

    POLNIASZEK R. P.

    J. Org. Chem. 55, 215, 1990

    DOI  Cited by (2)

Codes

  • NII Article ID (NAID)
    10011907694
  • NII NACSIS-CAT ID (NCID)
    AN0024521X
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    00379980
  • NDL Article ID
    6698235
  • NDL Source Classification
    ZP11(科学技術--化学・化学工業--有機化学・有機化学工業)
  • NDL Call No.
    Z17-256
  • Data Source
    CJP  NDL  J-STAGE 
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