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.

特别庞大的亲氧甲基铝双(2,6-二叔丁基-4-甲基苯酚) (MAD) 可用作路易斯酸性受体，与一系列羰基化合物、醚和环氧化物络合。通过使用低温13 C NMR光谱，发现MAD与含氧底物按照酰胺、醛、酮或酯、环氧化物和醚的顺序强烈配位。即使结构非常相似的羰基化合物也可以通过 MAD 轻松分离。这一观察结果使得基于 MAD 区分两种不同富马酸酯羰基的不对称富马酸酯的高度区域和立体控制的 Diels-Alder 反应成为可能。 MAD 的高识别能力已成功应用于通过使用 MAD 型聚合有机铝试剂的络合色谱法清洁分离结构非常相似的醚。该聚合物有机铝塔还可用作用于将环氧化物催化重排为羰基化合物的固态反应器。基于MAD分子识别化学，以三甲基铝和光学活性3,3'-双(三芳基硅基)联萘酚为原料，制备了一种新型手性有机铝试剂。这些手性有机铝试剂对于烯丙基乙烯基醚的不对称克莱森重排以及二烯和不饱和酯的不对称狄尔斯-阿尔德反应非常有用。

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)。

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

Keiji Maruoka、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-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)。

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。