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

在新反应、新不对称诱导反应和新药物种子化合物的开发过程中，我们在许多化合物的晶体结构中发现了S…O、S…N、S…S、S…π、π…π、CH…π和CH…O等非键相互作用。由于我们已经在血管紧张素II受体拮抗剂和新型碳青霉烯类抗生素双青霉烯中建立了分子内无键S…O相互作用，我们利用X射线晶体学分析和从头算MO计算揭示了新设计和合成的有机硫化合物中多种分子内无键S…X （S = O， N， S）相互作用。具体来说，在非手性和手性1,3-噻唑烷-2-硫基衍生物的脱硫自偶联反应中发现了S…S相互作用。利用x射线晶体学分析和从头MO计算，进一步澄清了酰基（或硫酰基）氨基噻二唑、酰基（或硫酰基）氨基噻二唑及其相关化合物的优势结构存在显著差异。在2-酰基-5-（2-卤代苯基）- 1,3,4 -噻二唑啉衍生物的X射线晶体结构中也发现了独特的分子内非键O…S…X （X = F, Cl, Br）相互作用，并通过模型化合物的从头计算澄清了在其可能的旋转异构体中具有S…卤素相互作用的结构是最稳定的。为了创造新的反应介质、新的功能材料和新的药物，合成了单、双、三噻唑类和萤火虫荧光素类化合物。在这些化合物中，类似地建立了非键S…X （X = O， S， N, Br）相互作用。利用手性亚砜与酰胺溶剂之间的分子间非键S…O相互作用，开发了具有高度化学选择性和立体选择性的不对称Pummerer反应。成功合成了以乙酰氨基噻二唑为悬垂基团的新型碳青霉烯类抗生素。少

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