緻密なルイス酸性制御を可能とするかご型金属錯体の創成と触媒反応への展開

• 安田 誠

  大阪大学大学院工学研究科応用化学専攻

• 馬場 章夫

  大阪大学大学院工学研究科応用化学専攻

書誌事項

タイトル別名

• Fine Tuning of Lewis Acidity by Cage-Shaped Ligand Structure toward Catalytic Reactions
• チミツ ナ ルイス サンセイ セイギョ オ カノウ ト スル カゴカタ キンゾク サクタイ ノ ソウセイ ト ショクバイ ハンノウ エ ノ テンカイ

抄録

Borate complexes that contain tridentate ligands tris(o-oxyaryl)methanes and -silanes were synthesized. These complexes had a cage-shaped structure around a boron center. The geometry of the structure determined the properties of the borates in which ligands were consistently bound to the metal center by chelation. Theoretical calculations suggested that the cage-shaped borates had a large dihedral angle (C_ipso-O-B-O) compared with open-shaped borates. The large angle leads to a greater Lewis acidity for cage-shaped borates. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity due to its smaller dihedral angle. The introduction of electron-withdrawing groups on the aryl moieties in the cage-shaped framework increased the Lewis acidity. The cage-shaped borates effectively catalyzed some organic transformations more than the open-shaped borate B(OPh)₃. Selective recognition of aromatic aldehyde over aliphatic aldehyde was accomplished in a catalytic manner by using cage-shaped borates with a π-pocket.

収録刊行物

• 有機合成化学協会誌

  有機合成化学協会誌 71 (12), 1294-1306, 2013

  公益社団法人 有機合成化学協会

キーワード

• Lewis acid
• geometric control
• catalyst
• borate
• recognition
• selectivity
• aromatic compounds
• cage-shape

詳細情報

• CRID: 1390001205339810304
• NII論文ID: 130003395359
• NII書誌ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.71.1294
• COI: 1:CAS:528:DC%2BC2cXks1aitw%3D%3D
• ISSN: 18836526
• ISSN: 00379980
• NDL書誌ID: 025071817
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I025071817
• 本文言語コード: ja
• データソース種別:
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