二座窒素配位中性型π-アリルパラジウム錯体の合成と触媒的シクロプロパン化反応への応用  [in Japanese] Synthesis of Neutral π-Allylpalladium Complexes having Bisnitrogen Ligands and Palladium-Catalyzed Cyclopropanation of Ketene Silyl Acetals with Allylic Acetates  [in Japanese]

Access this Article

Search this Article

Author(s)

    • 佐竹 彰治 SATAKE Akiharu
    • 奈良先端科学技術大学院大学物質創成科学研究科 Graduate School of Materials Science Nara Institute of Science and Technology(NAIST)

Abstract

Pyridinyl azole ligands, such as pyridinylpyrazoles, pyridinylimidazoles, and pyridinylpyrrole, were used as a new type of bisnitrogen ligands for π-allylpalladium complexes. Reaction of π-allylpalladium chloride dimer with pyridinyl azole ligands formed cationic π-allylpalladium complexes, which could be converted into neutral forms with bases. The neutral π-allylpalladium complexes worked as effective catalysts for cyclopropanation of ketene silyl acetals with allylic acetates whereas the cationic π-allylpalladium complex having bipyridyl ligand was almost unreactive. Reaction of cinnamyl acetate with ketene silyl acetal of ethyl 2-methylpropionate in the presence of the palladium-pyridinylimidazole catalyst and sodium acetate in DMSO gave a cyclopropane derivative selectively in a 83% yield. This reaction was also applicable for asymmetric cyclopropanation. When chiral pyrazole-palladium catalysts were used, chiral cyclopropane derivatives were obtained up to 54% ee. To examine the difference between cationic and neutral palladium complexes, X-ray diffraction analysis and temperature variable NMR studies were performed. Bond lengths between palladium and nitrogens of the neutral pyridinylimidazole complex were shorter than those of the cationic complex in the crystal structures. Further, kinetic constants of <I>syn-syn</I> and <I>anti-anti</I> exchange of the allyl moiety in the neutral complex was smaller than that in the case of cationic complex in DMF-<I>d</I><SUB>7</SUB> and DMSO-<I>d</I><SUB>6</SUB>. These results shows that palladium-nitrogen bonds of the neutral complex are stronger than that of the cationic complex, and these difference affects the reactivity for catalytic cyclopropanation.

Journal

  • Journal of Synthetic Organic Chemistry, Japan

    Journal of Synthetic Organic Chemistry, Japan 58(8), 736-744, 2000-08-01

    The Society of Synthetic Organic Chemistry, Japan

References:  32

  • <no title>

    辻二郎

    化学同人, 1997

    Cited by (1)

  • <no title>

    TSUJI J.

    Palladium Reagents and Catalysts, 1995

    Cited by (26)

  • <no title>

    TROST B. M.

    "Comprehensive Organic Synthesis", 1991

    Cited by (5)

  • <no title>

    KUROSAWA H.

    Bull. Chem. Soc. Jpn. 71, 973, 1998

    Cited by (2)

  • <no title>

    OHE K.

    J. Am. Chem. Soc. 116, 4125, 1994

    Cited by (2)

  • <no title>

    KADOTA J.

    Organometallics 19, 979, 2000

    Cited by (1)

  • <no title>

    HEGEDUS L. S.

    J. Org. Chem. 45, 5193, 1980

    Cited by (2)

  • <no title>

    HOFFMANN H. M. R.

    Angew. Chem., Int. Ed. Engl. 31, 234, 1992

    Cited by (3)

  • <no title>

    WILDE A.

    J. Chem. Soc., Chem. Commun. 1993, 615

    Cited by (1)

  • <no title>

    OTTE A. R.

    Angew. Chem., Int. Ed. Engl. 33, 1280, 1994

    Cited by (1)

  • <no title>

    HOFFMANN H. M. R.

    Angew. Chem., Int. Ed. Engl. 34, 100, 1995

    Cited by (1)

  • <no title>

    CARFAGNA C.

    J. Mol. Catal. 72, 19, 1992

    Cited by (2)

  • <no title>

    CARFAGNA C.

    J. Org. Chem. 56, 3924, 1991

    Cited by (2)

  • <no title>

    FORMICA M.

    J. Organomet. Chem. 448, C6, 1993

    Cited by (1)

  • <no title>

    SATAKE A.

    J. Am. Chem. Soc. 120, 10391, 1998

    Cited by (2)

  • <no title>

    JPHNSON L. K.

    J. Am. Chem. Soc. 117, 6414, 1995

    Cited by (1)

  • <no title>

    TROST B. M.

    Tetrahedron 33, 2615, 1977

    Cited by (6)

  • <no title>

    TROST B. M.

    J. Am. Chem. Soc. 97, 2354, 1975

    Cited by (1)

  • <no title>

    OSHIMA M.

    Organometallics 10, 1221, 1991

    Cited by (5)

  • <no title>

    AKERMARK B.

    Organometallics 6, 620, 1987

    Cited by (2)

  • <no title>

    MARTIN G. E.

    J. Nat. Pro. 63, 543, 2000

    Cited by (1)

  • <no title>

    SATAKE A.

    Chem. Lett. 1999, 49

    Cited by (1)

  • <no title>

    SATAKE A.

    Organometallics 18, 5108, 1999

    Cited by (1)

  • <no title>

    SATAKE A.

    Tetrahedron Lett. 40, 3597, 1999

    Cited by (1)

  • <no title>

    佐竹彰治

    第46回有機金属化学討論会要旨集 A205, 112, 1999

    Cited by (1)

  • <no title>

    ORGAN M. G.

    Tetrahedron Lett. 47, 8181, 1997

    DOI  Cited by (1)

  • Mechanism of nucleophilic attack on 1- and 2-bromo(π-allyl)palladium complexes

    ORGAN M. G.

    J. Am. Chem. Soc. 120, 9283-9290, 1998

    DOI  Cited by (2)

  • <no title>

    ARANYOS A.

    Organometallics 16, 1058, 1997

    DOI  Cited by (2)

  • <no title>

    BROOKHART M.

    J. Am. Chem. Soc. 114, 5895, 1992

    DOI  Cited by (1)

  • 磁場勾配パルス^<15>N HMBC法  [in Japanese]

    越野 広雪 , 鵜澤 洵

    化学と生物 33(4), 252-258, 1995-04-25

    References (32) Cited by (5)

  • <no title>

    SATAKE A.

    J. Organomet. Chem. 595(2), 208, 2000

    DOI  Cited by (1)

  • <no title>

    TSUJI J.

    Tetrahedron Lett. 42, 4783, 1984

    DOI  Cited by (1)

Codes

  • NII Article ID (NAID)
    10008821141
  • NII NACSIS-CAT ID (NCID)
    AN0024521X
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    00379980
  • NDL Article ID
    5431919
  • 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 
Page Top