Development of New Molecular Recognition Chemistry using Organoaluminums

利用有机铝开发新型分子识别化学

• 批准号: 03453100
• 负责人: YAMAMOTO Hisashi
• 金额: $ 4.42万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453100/
• 关键词: Lewis Acidic Receptor; Organoaluminums; Molecular Recognition; Complexation Chromatography; Diels-Alder Reaction; Chiral Organoaluminums; Binaphthols; Asymmetric Claisen Rearrangement; 不斉ディールズ・アルダー反応; ルイス酸型レセプタ-; 複合体形成クロマトグラフィ-; ディ-ルズ・アルダ-反応

Exceptionally bulky, oxygenophilic methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) can be utilized as a Lewis acidic receptor for complexation with a series of carbonyl compounds, ether, and epoxides. By using low-temperature ^<13>C NMR spectroscopy, MAD was found to coordinate strongly to oxygen-containing substrates in the order of amides, aldehydes, ketones or esters, epoxides, and ethers. Even structurally very similar carbonyl compounds can be easily separated by MAD. This observation enabled the highly regio- and stereocontrolled Diels-Alder reaction of unsymmetrical fumarates based on the discrimination of two different fumarate carbonyls with MAD. The high recognition ability of MAD is successfully applied to the clean separation of structurally very similar ethers by complexation chromatography using MAD-type, polymeric organoaluminum reagents. This polymeric organoaluminum column is also employable as solid-state reactor for catalytic rearrangement of epoxides to carbonyl compounds. Based on the molecular recognition chemistry with MAD, a new type of chiral organoaluminum reagents have been developed which are prepared from trimethylaluminum and optically active 3,3'-bis(triarylsilyl)binaphthols. These chiral organoaluminum reagents are highly useful for asymmetric Claisen rearrangement of allylic vinyl ethers and asymmetric Diels-Alder reaction of dienes and unsaturated esters.

异常笨重的含氧甲基铝铝双（2,6-二丁基-4-甲基苯基氧化物）（MAD）可用于刘易斯酸性受体，以与一系列的羰基化合物，以太，以太乙醚，和氧化氧化物进行络合。通过使用低温 ^<13> c NMR光谱，发现MAD可以在酰胺，醛，醛，酮或酯，环氧化物和醚的顺序上与含氧的底物进行强烈的协调。即使在结构上非常相似的羰基化合物也很容易被疯狂分离。这一观察结果使非对称富马酸群的高度区域和立体控制的Diels-Alder反应基于对两种不同的富马酸羰基的歧视。 MAD的高识别能力成功地应用于使用MAD型，聚合有机化试剂的络合色谱法清洁结构非常相似的醚分离。该聚合物有机金属柱也可作为固态反应堆，用于将环氧化物催化重排向羰基化合物。基于MAD的分子识别化学，已经开发了一种新型的手性有机毛试剂，该试剂是由三甲基铝和光学活性的3,3'-双基（三叶二烯丙基）双硫醇制备的。这些手性有机毛试剂对于烯丙基乙烯基醚的不对称claisen重排和二enes和不饱和酯的不对称Diels-Alder反应非常有用。

项目成果

Keiji Maroka,Susumu Saito,Hisashi Yamamoto: "Discrimination of Two Different Ester Carbonyls with MAD:Application to the Regio-and Stereocontrolled Diels-Alder Reaction of Unsymmetrical Fumarates" Jounal of the American Chemical Society. 114. 1089-1090 (1

Keiji Maroka、Susumu Saito、Hisashi Yamamoto：“用 MAD 区分两种不同的酯羰基：在不对称富马酸酯的区域和立体控制 Diels-Alder 反应中的应用”美国化学会杂志。

長原 滋,山本 尚,丸岡 啓二: "ルイス酸型レセプターによる分子認識" 化学. 46. 204-205 (1991)

Shigeru Nagahara、Hisashi Yamamoto、Keiji Maruoka：“路易斯酸受体的分子识别”化学 46. 204-205 (1991)。

Shigeru Nagahara,Keiji Maruoka,Hisashi Yamamoto: "A Facile Workup-Free Catalytic Rearrangement of Epoxides on Immobilized Organoaluminum Columns" Chemistry Letters. 1193-1196 (1992)

Shigeru Nagahara、Keiji Maruoka、Hisashi Yamamoto：“固定有机铝柱上环氧化物的简便免后处理催化重排”化学快报。

Keiji Maruoka,Junko Sato,Hisashi Yamamoto: "Practical Asymmetric Synthesis of Both Erythro and threo Aldols:Unusual Effect of Silyl Groups" Journal of the American Chemical Society. 113. 5449-5450 (1991)

Keiji Maruoka、Junko Sato、Hisashi Yamamoto：“赤式和苏式醛醇的实用不对称合成：甲硅烷基的不寻常效应”美国化学会杂志。

長原 滋,山本 尚,丸岡 啓二: "ルイス酸型レセプタ-による分子認識" 化学. 46. 204-205 (1991)

Shigeru Nagahara、Hisashi Yamamoto、Keiji Maruoka：“路易斯酸受体的分子识别”化学 46. 204-205 (1991)。