Regiocontrol of ring cleavage and cycloaddition of oxiranes catalyzed by organotin- and organoantimony halides

有机锡和有机锑卤化物催化环氧乙烷开环和环加成的区域控制

基本信息

批准号：
62550613
负责人：
BABA Akio
金额：
$ 1.28万
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 (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

Oxiranes are industrially available and useful reagents, but too unstable to treat under acidic or basic conditions. Complete regiocontrol of the oxirane-ring cleavage, so, is a significant and serious problem in modern chemistry. In this study, following results were obtained on this subject.1. Cycloaddition of monosubstituted oxiranes with heterocumulenes.In the presence of organotin halide-base complex, the reactions with isocyanates, carbodiimides proceeded via -cleavage of oxirane to furnish the corresponding 3,5-disubstituted heterocyclic compounds under very mild conditions. On the contrary, Ph_4SbI promoted the -cleavaged reaction of oxiranes to gave isomeric heterocyclic compounds, 3,4-disubstituted ones, in high yields. The latter type of cycloaddition has not been reported so far. On the other hand, in the reaction of ketene with oxiranes SN catalyst and SB catalyst gave 1,3-dioxolane and -lactone derivatives, respectively.Thus, compensatable use of the both catalysts would be expected to be adopted widely in organic synthesis.2. Reaction of amines with oxiranes catalyzed by Ph_4SbOTf.Tile reaction was effected under complete anhydrous conditions in the presence of catalytic amounts of Ph_4SbOTf. Moreover, this catalyst allowed the use of an equimolar amount of amine, although excess amounts have been indespensable in conventional systems.

食氧是工业上可用的，有用的试剂，但过于不稳定，无法在酸性或基本条件下治疗。因此，在现代化学中，阿氧烷环裂解的完整控制是一个重大而严重的问题。在这项研究中，在该主题上获得了以下结果。1。在存在器官蛋白卤化物基碱复合物的存在下，单叠构成的氧胆汁的环加成，与异氰酸酯的反应，碳纤维二二酰亚胺通过氧雷亚的切割来提供相应的3,5-5-5-二蛋白蛋白的杂质化合物。相反，PH_4SBI以高产量为异构体异构化合物，3,4-二取代的化合物促进了对异构体杂环化合物的分裂反应。到目前为止，尚未报道后一种类型的环加成。另一方面，在酮与氧杂种SN催化剂和SB催化剂的反应中，分别得到1,3-二氧烷和 - 乳酮衍生物的反应。因此，预计在有机合成中，可补偿的两种催化剂的使用将被广泛采用。2。在完全无水条件下，在存在催化量的PH_4SBOTF的情况下，在完全无水条件下作用胺与用PH_4SBOTF催化的胺反应。此外，该催化剂允许使用等摩尔量的胺，尽管在常规系统中却无数含量。