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

• 佐竹 彰治

  奈良先端科学技術大学院大学物質創成科学研究科

書誌事項

タイトル別名

• Synthesis of Neutral .PI.-Allylpalladium Complexes having Bisnitrogen Ligands and Palladium-Catalyzed Cyclopropanation of Ketene Silyl Acetals with Allylic Acetates.
• 2ザチッソハイイ チュウセイガタ パイ アリルパラジウム サクタイ ノ ゴウセイ ト ショクバイテキ シクロプロパンカ ハンノウ エ ノ オウヨウ

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 syn-syn and anti-anti exchange of the allyl moiety in the neutral complex was smaller than that in the case of cationic complex in DMF-d₇ and DMSO-d₆. 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

  公益社団法人 有機合成化学協会

キーワード

• pyrazole
• imidazole
• pyrrole
• ligand
• π-allylpalladium
• cationic
• neutral
• catalyst
• cyclopropane
• ketene silyl acetal
• allyl acetate
• asymmetric synthesis

詳細情報

• CRID: 1390001205279080704
• NII論文ID: 10008821141
• NII書誌ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.58.736
• ISSN: 18836526
• ISSN: 00379980
• NDL書誌ID: 5431919
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I5431919
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • NDL
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  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可