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 Synthesis of Neutral π-Allylpalladium Complexes having Bisnitrogen Ligands and Palladium-Catalyzed Cyclopropanation of Ketene Silyl Acetals with Allylic Acetates

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著者

    • 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)

抄録

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.

収録刊行物

  • 有機合成化学協会誌

    有機合成化学協会誌 58(8), 736-744, 2000-08-01

    The Society of Synthetic Organic Chemistry, Japan

参考文献:  32件中 1-32件 を表示

  • <no title>

    辻二郎

    化学同人, 1997

    被引用文献1件

  • <no title>

    TSUJI J.

    Palladium Reagents and Catalysts, 1995

    被引用文献26件

  • <no title>

    TROST B. M.

    "Comprehensive Organic Synthesis", 1991

    被引用文献5件

  • <no title>

    KUROSAWA H.

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

    被引用文献2件

  • <no title>

    OHE K.

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

    被引用文献2件

  • <no title>

    KADOTA J.

    Organometallics 19, 979, 2000

    被引用文献1件

  • <no title>

    HEGEDUS L. S.

    J. Org. Chem. 45, 5193, 1980

    被引用文献2件

  • <no title>

    HOFFMANN H. M. R.

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

    被引用文献3件

  • <no title>

    WILDE A.

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

    被引用文献1件

  • <no title>

    OTTE A. R.

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

    被引用文献1件

  • <no title>

    HOFFMANN H. M. R.

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

    被引用文献1件

  • <no title>

    CARFAGNA C.

    J. Mol. Catal. 72, 19, 1992

    被引用文献2件

  • <no title>

    CARFAGNA C.

    J. Org. Chem. 56, 3924, 1991

    被引用文献2件

  • <no title>

    FORMICA M.

    J. Organomet. Chem. 448, C6, 1993

    被引用文献1件

  • <no title>

    SATAKE A.

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

    被引用文献2件

  • <no title>

    JPHNSON L. K.

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

    被引用文献1件

  • <no title>

    TROST B. M.

    Tetrahedron 33, 2615, 1977

    被引用文献6件

  • <no title>

    TROST B. M.

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

    被引用文献1件

  • <no title>

    OSHIMA M.

    Organometallics 10, 1221, 1991

    被引用文献5件

  • <no title>

    AKERMARK B.

    Organometallics 6, 620, 1987

    被引用文献2件

  • <no title>

    MARTIN G. E.

    J. Nat. Pro. 63, 543, 2000

    被引用文献1件

  • <no title>

    SATAKE A.

    Chem. Lett. 1999, 49

    被引用文献1件

  • <no title>

    SATAKE A.

    Organometallics 18, 5108, 1999

    被引用文献1件

  • <no title>

    SATAKE A.

    Tetrahedron Lett. 40, 3597, 1999

    被引用文献1件

  • <no title>

    佐竹彰治

    第46回有機金属化学討論会要旨集 A205, 112, 1999

    被引用文献1件

  • <no title>

    ORGAN M. G.

    Tetrahedron Lett. 47, 8181, 1997

    DOI 被引用文献1件

  • 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 被引用文献2件

  • <no title>

    ARANYOS A.

    Organometallics 16, 1058, 1997

    DOI 被引用文献2件

  • <no title>

    BROOKHART M.

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

    DOI 被引用文献1件

  • 磁場勾配パルス^<15>N HMBC法

    越野 広雪 , 鵜澤 洵

    化学と生物 33(4), 252-258, 1995-04-25

    参考文献32件 被引用文献5件

  • <no title>

    SATAKE A.

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

    DOI 被引用文献1件

  • <no title>

    TSUJI J.

    Tetrahedron Lett. 42, 4783, 1984

    DOI 被引用文献1件

各種コード

  • NII論文ID(NAID)
    10008821141
  • NII書誌ID(NCID)
    AN0024521X
  • 本文言語コード
    JPN
  • 資料種別
    ART
  • ISSN
    00379980
  • NDL 記事登録ID
    5431919
  • NDL 雑誌分類
    ZP11(科学技術--化学・化学工業--有機化学・有機化学工業)
  • NDL 請求記号
    Z17-256
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    CJP書誌  NDL  J-STAGE 
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