Reaction control of cyclic ethers by new versatile catalysts and its application

新型多功能催化剂环醚反应控制及其应用

• 批准号: 60430022
• 负责人: MATSUDA Haruo
• 金额: $ 22.4万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60430022/
• 关键词: oxirane; isocyanate; carbodiimide; cycloaddition; regiocontrol; organotin halide complexes; 有機スズハライド錯体; オキシラン; オキセタン; イソシアナート; オキサジノン; 3,4-ジ置換オキサゾリドン

The cycloaddition of oxiranes with heterocumulenes such as isocyanates and carbodiimides has been ardently investigated. Although a variety of catalysts for this reaction have been reported, the problems such as low yields and severe reaction conditions have not been resolved as yet. Now, this our project has given one resolution in terms of developing novel catalysts; organotin iodide-Lewis base complexes(1), organotin iodide-onium halide salts complexes(2) and tetraphenylstibonium iodide(3). These catalysts very effectively promoted the cycloadditon of under very mild conditions to produce many kinds of heterocyclic compounds in excellent yield. Advantages and features of these catalysts are as follows(a-c);(a) The cycloadditions complete within few hours at room temperature.(b) The catalysts 1 and 2 selectively promote the -cleavage cycloaddition of monosubstituted oxiranes. On the contrary, the catalyst 3 promotes the -cleavage one which has been unsuccessful by conventional catalysts at all. The both reactions could be carried out for the same reactants under similar reaction conditions, and so these catalysts can be used compensationally.(c) These catalysts are so nearly neutral that the oxiranes bearing labile substituents are applicable to this cycloaddition.

环氧乙烷与异氰酸酯和碳二亚胺等杂累积烯的环加成反应已得到广泛研究。虽然已经报道了用于该反应的各种催化剂，但是诸如产率低和反应条件苛刻的问题尚未得到解决。目前，我们的项目在开发新型催化剂方面给出了一个解决方案：碘化有机锡-路易斯碱配合物（1），碘化有机锡-卤化鎓盐配合物（2）和碘化四苯基锑（3）。这些催化剂能在温和的条件下有效地促进环加成反应，以高产率合成多种杂环化合物。这些催化剂的优点和特征如下（a-c）：（a）环加成在室温下在几小时内完成。(b)催化剂1和2选择性地促进单取代环氧乙烷的开环加成反应。相反，催化剂3促进了传统催化剂根本不成功的裂解。这两种催化剂可以在相似的反应条件下对相同的反应物进行，因此可以互补使用。(c)这些催化剂几乎是中性的，因此带有不稳定取代基的环氧乙烷也适用于这种环加成反应。

项目成果

I.Shibata: J.Org.Chem.51. 2177-2184 (1986)

I.Shibata：J.Org.Chem.51。

A.Baba: Tetrahedron Lett.26. 5167-5170 (1985)

A.Baba：四面体 Lett.26。

A.Baba: Tetrahedron Lett.27. 77-80 (1986)

A.Baba：四面体 Lett.27。

A. Baba: "Novel Use of Organotin Halide-Base Complex in Organic Synthesis; Cycloaddition Reaction of Oxetane with Isocyanates" Tetrahedron Lett.26. 5167-5170 (1985)

A. Baba：“有机锡卤化物基络合物在有机合成中的新用途；氧杂环丁烷与异氰酸酯的环加成反应”Tetrahedron Lett.26。

A. Baba: "Unusual Cycloaddition of Oxiranes with Isocyanates Catalyzed by Tetraphenylstibonium Iodide: Selective Formation of 3,4-Disubstituted Oxazolidinones" Tetrahedron Lett.27. 77-80 (1986)

A. Baba：“四苯基碘化锑催化的环氧乙烷与异氰酸酯的异常环加成反应：选择性形成 3,4-二取代的恶唑烷酮”Tetrahedron Lett.27。