Construction of New Reaction Media and Its Application Based on the Non-bonded Interaction Concept

基于非键相互作用概念的新型反应介质的构建及其应用

• 批准号: 12470482
• 负责人: NAGAO Yoshimitsu
• 金额: $ 9.22万
• 依托单位: The University of Tokushima
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12470482/
• 关键词: non-bonded interaction; molecular recognition; reaction media; organosulfur compound; X-ray analysis; Pummerer reaction; carbapenem; ab initio; 有機イオウ化合物; チアジアゾリン; チアゾール; 反応メディア; アシルアミノチアジアゾール; アシルイミノチアジアゾリン

In the course of development of new reactions, new asymmetric induction reactions, and new seed compounds toward drugs, we have found several non-bonded interactions such as S…O, S…N, S…S, S…π, π…π, CH…π, and CH…O in the crystallographic structures of many compounds. Since we have established an intramolecular non-bonded S…O interaction in the molecules of angiotensin II receptor antagonists and a new carbapenem antibiotic, biapenem, we have revealed many kinds of intramolecular non-bonded S…X (S = O, N, S) interactions in newly designed and synthesized organosulfur compounds by utilizing X-ray crystallographic analysis and ab initio MO calculation. Specifically, the S…S interaction was recognized in the compounds obtained from desulfurirative self-coupling reaction of achiral and chiral 1,3-thiazolidine-2-thiorie derivatives. Remarkable discrepancy in the predominant structures of acyl(or thioacyl) aminothiadiazoles, acyl(or thioacyl) aminooxadiazoles, and the related compounds was cl … More arified by utilizing X-ray crystallographic analyses and ab initio MO calculation. Unique and novel intramolecular non-bonded O…S…X (X = F, Cl, Br) interactions have also recognized in the X-ray crystallographic structures of 2-acylimino-5-(2-halophenyl)- 1, 3, 4- thiadiazoline derivatives, and it was clarified in terms of the ab initio MO calculation of the model compounds that the structure bearing an S…halogen interaction is most stable in their possible rotational isomers. In order to create new reaction media, new functional materials, and new drugs, mono-, bi-, tri-thiazoles and firefly luciferin-like compounds were synthesized. In these compounds, non-bonded S…X (X = O, S, N, Br) interactions were similarly established. Highly chemo- and stereoselective asymmetric Pummerer reactions were developped by utilizing inter molecular non-bonded S…O interaction between chiral sulfoxides and amide solvents. Syntheses of new carbapenem antibiotics bearing acyliminothiadiazolines as the pendant moiety, were successfully achieved. Less

在对药物的新反应、新的不对称诱导反应和新的种子化合物的发展过程中，我们发现了几个非键的相互作用，如S…O，S…N，S…S、S…π，π…π，CH…π和CH…O在许多化合物的晶体结构中。由于我们已经建立了分子内非键S…血管紧张素II受体拮抗剂与新的碳青霉烯类抗生素比阿培南分子间的相互作用，揭示了多种分子内非结合的S…X(S=O，N，S)在新设计合成的有机硫化合物中的相互作用具体地说，S…无手性和手性1，3-噻唑烷-2-硫代衍生物的脱硫自偶联反应得到的化合物中存在S相互作用。酰基(或硫代酰基)氨基噻二唑与酰基(或硫代酰基)氨基恶二唑的主要结构有显著差异，相关化合物为CL-…通过X-射线晶体分析和从头算分子轨道计算，得到了更准确的结果。独特新颖的分子内非键O-…S…在2-酰亚氨基-5-(2-卤苯基)-1，3，4-噻二唑啉类化合物的X-射线晶体结构中也发现了X(X=F，Cl，Br)相互作用，并通过模型化合物的从头算证明了该结构含有S…在可能的旋转异构体中，卤素相互作用最稳定。为了创造新的反应介质、新的功能材料和新的药物，人们合成了单、双、三噻唑和萤火虫类荧光素类化合物。在这些化合物中，非键合的S…X(X=O，S，N，Br)相互作用也同样建立。利用分子间非键S…发展了高度化学和立体选择性的不对称Pummerer反应O手性亚砜与酰胺类溶剂之间的相互作用。成功地合成了以酰亚胺并噻二唑为侧链的新型碳青霉烯类抗生素。较少

项目成果

Yoshimitsu Nagao: "Remarkable Discrepancy in the Predominant Structures of Acyl(or thioacyl)amino-thiadiazoles, Acyl(or thioacyl)aminoozadiazoles and Related Compounds"Tetrahedron Letters. 43・9. 1709-1712 (2002)

Yoshimitsu Nagao：“酰基（或硫代酰基）氨基噻二唑、酰基（或硫代酰基）氨基恶二唑及相关化合物的主要结构的显着差异”Tetrahedron Letters 43・9（2002）。

Nagao,Yoshimitsu: "Highly Chemoselective Pummerer Reactions of Sulfinyldiacetic Acid Derivative"Tetrahedron Letters. 43-8. 1519-1522 (2002)

Nagao，Yoshimitsu：“亚磺酰二乙酸衍生物的高度化学选择性普默勒反应”四面体字母。

Nagao,Yoshimitsu: "Remarkable Discrepancy in the Predominant Structures of Acyl(or Thioacyl) aminothiadiazoles, Acyl(or Thioazyl)aminooxadiazoles and Related Compounds Having the Potential for Rotational, Geometrical and Tautomeric Isomerism"Tetrahedron L

Nagao, Yoshimitsu：“酰基（或硫代酰基）氨基噻二唑、酰基（或硫代酰基）氨基恶二唑以及具有旋转、几何和互变异构潜力的相关化合物的主要结构的显着差异”四面体 L

Yoshimitsu Nagao: "Highly Chemoselective Pummerer Reactions of Sulfinyldiacetic Acid Derivative"Tetrahedron Letters. 43・8. 1519-1522 (2002)

Yoshimitsu Nagao：“亚磺酰二乙酸衍生物的高度化学选择性普默勒反应”四面体快报 43・8（2002）。

Yoshimitsu Nagao: "Synthesis and Antibacterial Activity of New 1β-Methylcarbaoenems Having the Potential for Intramolecular Nonbonded S…O Interactions"Chemical & Pharmaceutical Bulletin. 49・12. 1660-1661 (2001)

Yoshimitsu Nagao：“具有分子内非键合 S…O 相互作用潜力的新型 1β-甲基碳烯烯的合成和抗菌活性”《化学与制药通报》49・12（2001 年）。