Development of a new molecular recognition chemistry using Lewis acidic receptors

使用路易斯酸性受体开发新的分子识别化学

• 批准号: 06403024
• 负责人: YAMAMOTO Hisashi
• 金额: $ 21.18万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06403024/
• 关键词: Lewis acidic receptor; Aluminum reagent; Designer Lewis acid; Lewis base; Selective organic synthesis; Molecular recognition chemistry; Lewis acid-base complex; ルイス塩基複合体; 有機アルミニウム; 複合体形成クロマトグラフィー

The fascination of molecular recognition chemistry is extending continuously, especially as host-guest systems which mimic biologically occurring compounds exhibiting catalytic activities like enzymes. The discovery of crown ethers and cryptands and their inclusion systems by Prof. Lehn and Cram led them to be the winners of the Nobel Prize, and most of these systems are constituted by hydrogen-bonding networks between host and guest molecules. Comparing with these weak interactions, relatively strong coordination bonding between Lewis acidic receptors and Lewis bases has received less attention for molecular recognition, and has never been used for selective organic synthesis.In this context, we have developed several bulky organoaluminum reagents which have sterically hindered phenoxide ligands. These bulky aluminum reagents are monomeric in solution, thereby possess strong Lewis acidity to bind a variety of heteroatom-containing substrates such as carbonyl, carboxyl and amide compounds. The complexation is sometimes stereo-, regio-, and chemoselective, leading to selective organic reactions which could not be realized with other ordinary Lewis acicls such as AlCl_3, SnCl_4, BF_3, and TiCl_4. In particular, aluminum tris(2,6-diphenylphenoxide(ATPH) was explored recently for obtaining unprecedented reactivity and selectivity n several reactions. 1. Conjugate addition of carbanions to alpha, beta-unsaturated aldehydes 2. Exo-selective Diels-Alder reactions 3. Stereo-and asymmetric Claisen rearrangement 4.1,6-Addition to aromatic carbonyl substrates.

分子识别化学的魅力正在不断扩大，特别是作为主客体系统，模拟生物存在的化合物表现出催化活性，如酶。Lehn和Cram教授发现的冠醚和穴醚及其包合体系使他们成为诺贝尔奖的获得者，这些体系大多数是由主客体分子之间的氢键网络构成的。与这些弱相互作用相比，刘易斯酸受体与刘易斯碱之间较强的配位键在分子识别中的应用较少，在选择性有机合成中的应用也较少。这些大体积铝试剂在溶液中是单体，因此具有强的刘易斯酸性以结合各种含杂原子的底物，例如羰基、羧基和酰胺化合物。这种络合作用有时是立体选择性、区域选择性和化学选择性的，从而导致选择性的有机反应，这是用其它普通的刘易斯酸如AlCl_3、SnCl_4、BF_3和TiCl_4所不能实现的。特别地，三（2，6-二苯基苯酚）铝（ATPH）最近被探索用于在若干反应中获得前所未有的反应性和选择性。1.碳负离子与α，β-不饱和醛的共轭加成2。外选择性Diels-Alder反应3.立体和不对称克莱森重排4.1，6-加成到芳族羰基底物。

项目成果

丸岡 啓二: "Molecular Design of a Chiral Lewis Acid the Asymmetric Claisen Rearrangement" J.Am.Chem.Soc.117. 1165-1166 (1995)

Keiji Maruoka：“手性路易斯酸不对称克莱森重排的分子设计”J.Am.Chem.Soc.1165-1166 (1995)。

丸岡啓二: "Virtualy Complete Blocking at αβ-Unsaturated Aldehydes Carbonyls by Complexation with Aluminum Tris (216-diphenylphenoxide)" J. Am. Chem. Soc.116(9). 4131-4132 (1994)

Keiji Maruoka：“通过与三 (216-二苯酚铝) 络合几乎完全封闭 αβ-不饱和醛羰基”J. Am. 116(9)。

K.Maruoka, M.Ito, H.Yamamoto: "Unprecedented Nucleophilic Addition of Organolithiums to Aromatic Aldehydes and Ketones by Complexation with Aluminum Tris(2,6-diphenylphenoxide)" J.Am.Chem.Soc.117(35). 9091-9092 (1995)

K.Maruoka、M.Ito、H.Yamamoto：“通过与三(2,6-二苯酚铝)铝络合将有机锂前所未有地亲核加成到芳香醛和酮”J.Am.Chem.Soc.117(35)。

丸岡 啓二: "Unprecedented Nucleophilic Addition of Organolithiums to Aromatic Aldehydes and Ketones by Complexation with Aluminum Tris(2,6-diphenylphenoxide)" J.Am.Chem.Soc.117. 9091-9092 (1995)

Keiji Maruoka：“通过与三(2,6-二苯酚铝)铝络合将有机锂前所未有地亲核加成”J.Am.Chem.Soc.117 (1995)。

斎藤進: "逆合成" 化学. 51・1. 34-36 (1996)

Susumu Saito：“逆合成”化学51・1（1996）。