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.

分子识别化学的迷恋正在连续延伸，尤其是作为宿主 - 圈系统，它们模仿生物学上发生的化合物表现出催化活性，例如酶。 Lehn和Cram教授对皇冠醚和加密系统的发现及其包容系统使他们成为诺贝尔奖的获奖者，其中大多数系统都是由宿主和来宾分子之间的氢键网络构成的。与这些弱相互作用相比，刘易斯酸性受体和刘易斯碱之间的相对较强的配位键对分子识别受到了较少的关注，并且从未用于选择性有机合成。在这种情况下，我们已经开发了几种笨重的有机毛反应。这些笨重的铝试剂在溶液中是单体的，因此具有较强的刘易斯酸度，以结合各种含杂种剂的底物，例如羧基，羧基和酰胺化合物。络合有时是立体，区域和化学选择性的，导致选择性有机反应，这些反应无法与其他普通的刘易斯ACIC（例如ALCL_3，SNCL_4，BF_3，BF_3和TICL_4）实现。特别是，最近探索了Tris铝（2,6-二苯基苯基氧化物（ATPH），以获得前所未有的反应性和选择性n多种反应。1。在α-未饱和的β-未饱和醛中加入carbanions carbanions添加碳纤维，β-未饱和的醛固醛2。 4.1,6-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)。

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)。

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)。

Keiji Maruoka: "Virtually Complete Blocking of α、β-Unsaturated Aldehyde Carbonyls by Complexation with Aluminum Tris (2.6-diphenylphcnoxidc)" Journal of the American Chemical Society. 116. 4131-4132 (1994)

Keiji Maruoka：“通过与三（2.6-二苯基苯氧基）铝络合几乎完全阻断 α,β-不饱和醛羰基”美国化学会杂志 116. 4131-4132 (1994)。