Self-Assembly of Molecules in Crystal and Its Application to Selective Organic Synthesis

晶体中分子的自组装及其在选择性有机合成中的应用

• 批准号: 04453102
• 负责人: TODA Fumio
• 金额: $ 4.35万
• 依托单位: Ehime 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: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453102/
• 关键词: Self-Assembly; Moleclular Crystal; Selective Synthesis; Chiral Control; 選択的反応; 固相反応; 溶媒効果; ホスト化合物; X線解析; 包接結晶; 光反応

It was found that self-assembly of molecules in crystal is not always adequate for a selective reaction. However, we found that when molecules of reactant are assembled together with host molecules, the former are arranged regularly and the solid state reaction proceeds selectively.For example, photoirradiation of a 1 : 1 inclusion complex powder of N-benzoylmethyl-delta-valerolactam (2) and the optically active host (1) which had been derived from tartaric acid, in a water suspension under stirring gave optically almost pure bicyclic delta-valerolactam alcohol. X-ray crystal structure analysis of the inclusion complex showed that molecules of 2 and 1 are self-assembled to form 1 : 1 inclusion complex in which precise chiral recognition occurs. According to the chiral recognition, attack of reagent from the front and rear side of the reactant is controlled and single product is obtained. Inclusion crystals of various derivatives of 2 with 1 were also prepared and their photoreactions gave optically pure photocyclization products.

发现晶体中分子的自组装并不总是适合于选择性反应。然而，我们发现，当反应物分子与主体分子组装在一起时，前者是规则排列的，并且固态反应选择性地进行。1 N-苯甲酰基甲基-δ-戊内酰胺（2）和衍生自酒石酸的光学活性主体（1）的包合物粉末，在水悬浮液中搅拌，得到光学上几乎纯的双环δ-戊内酰胺醇。X-射线晶体结构分析表明，2和1的分子自组装形成1：1的包合物，包合物中存在精确的手性识别。通过手性识别，控制试剂从反应物的前后侧进攻，得到单一产物。还制备了2与1的各种衍生物的包结晶体，它们的光反应得到光学纯的光环化产物。

项目成果

Fumio Toda, Koichi Tanaka, Zafra Stein, Israel Gold: "Structure and Inclusion Characteristics of (R,R)-(-)-2,3-Dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol" J.Chem. Soc. Perkin Trans.2. 2359-2361 (1993)

Fumio Toda、Koichi Tanaka、Zafra Stein、以色列金奖：“(R,R)-(-)-2,3-二甲氧基-1,1,4,4-四苯基丁烷-1,4-二醇的结构和包含物特征”

Koichi Tanaka: "Control of the Stereochemistry in the Photocyclisation of Acrylanilides to 3,4-Dihydroquinolin-2(1H)-ones" J. Chem. Soc., Chem. Commun.1053-1054 (1992)

Koichi Tanaka：“控制丙烯酰苯胺光环化为 3,4-二氢喹啉-2(1H)-酮的立体化学”J. Chem。

戸田芙三夫: "Structure and Inclusion Charactristics of(R,R)-(-)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol" J.Chem.Soc.Perkin Trans.2. 2359-2361 (1993)

Fuzo Toda：“(R,R)-(-)-2,3-二甲氧基-1,1,4,4-四苯基丁烷-1,4-二醇的结构和包含特征”J.Chem.Soc.Perkin Trans。 2. 2359-2361 (1993)

Koichi Tanaka: "Efficient Optical Resolution of Some Key Compounds of Prostaglandin Synthesis" J. Chem. Soc. Perkin Trans. 1. 517-520 (1992)

Koichi Tanaka：“前列腺素合成的一些关键化合物的有效光学拆分”J. Chem。

Fumio Toda: "Molecular Recognition in the Solid State" JAI Press Inc. (London), 195 (1992)

Fumio Toda：“固态分子识别”JAI Press Inc.（伦敦），195（1992）