Synthesis and Reactions of Novel Boron-containing Double-bond Compounds by Taking Advantage of Steric Protection

利用空间保护的新型含硼双键化合物的合成与反应

基本信息

批准号：
09440216
负责人：
TOKITOH Norihiro
金额：
$ 8.96万
依托单位：
KYUSHU UNIVERSITY (1998)The University of Tokyo (1997)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

Very little is reported for the synthesis of stable boron-containing double-bond compounds because they are highly reactive, On the other hand, we have succeeded in the synthesis of highly reactive species by taking advantage of kinetic stabilization using effective steric protection group, 2,4,6-tris[bis(trimethylsilyl)-methyl]phenyl (Tbt) group. In this project, as the first stage for the development of the chemistry of multiple-bonded compounds containing group 13 elements, we planned the synthesis of stable thioxoborane 1 [TbtB=S] and diborene 2 [TbtB=BTbt] by taking advantage of Tbt group leading to the elucidation of their properties.We succeeded in the synthesis of the first stable dimercaptoborane 3 [TbtB(SH)_2]. Reactions of 3 with various group 4, 14 or 15 metal dihalides gave the corresponding 1,3,2,4-dithiametallaboretane derivatives 4, and the differences in their structures and properties were systematically investigated. Thermolysis of 1,3,2,4-dithiastannaboretane 4a [TbtBS_2SnPh_2] resulted in the formation of the expected thioxoborane 1 via [2+2]retrocycloaddition. Thioxoborane 1 reacted with 1 , 3-dienes to afford the corresponding [2+4]cycloadducts 5, which was found to regenerate 1 via [2+4]retrocycloaddition on heating.Reaction of 4a with dimethylsulfoxide (DMSO) gave the oxoborane-DMSO complex 6 [TbtB=O-DMSO], the first stable oxoborane-Lewis base complex. Thermolysis of 6 resulted in the formation of the corresponding oxoborane [TbtB=O].We have also succeeded in the generation of selenoxoborane [TbtB=Se] by thermolysis of the corresponding 1,3,2,4-diselenastannnaboretane derivative.Although we have not succeeded in the synthesis of diborene 2, the other target molecule in this project, yet, we believe that the synthesis of 2 can be achieved on the basis of the knowledge about boron-group 16 element double-bond compounds obtained in this project.

对于稳定的含硼的双键化合物的综合而言，几乎没有报道很少，因为它们具有高反应性，另一方面，我们通过使用有效的空间保护组，2，4,6-6- tris [bis（trimethylsilyl）[trimethylsilyl） - 米甲基]苯基（TBT）组成了高反应性物种的合成。在这个项目中，作为开发包含13组元素的多键化合物化学性质的第一阶段，我们计划合成稳定的硫豆异烷1 [tbtb = s]和Diborene 2 [tbtb = btbt] [tbtb = btbt]，通过利用TBT组的优势，使TBT组的优势使他们的属性保持稳定。 [TBTB（SH）_2]。 3与各组4、14或15个金属迪哈里德山脉的反应给出了相应的1,3,2,4-二苯甲酸衍生物衍生物4，并且系统地研究了其结构和特性的差异。 1,3,2,4-二硫代氨基甲烷4A [TBTBS_2SNPH_2]的热解会导致通过[2+2] retrocycloadition形成预期的硫代毛素1。 Thioxoborane 1 reacted with 1 , 3-dienes to afford the corresponding [2+4]cycloadducts 5, which was found to regenerate 1 via [2+4]retrocycloaddition on heating.Reaction of 4a with dimethylsulfoxide (DMSO) gave the oxoborane-DMSO complex 6 [TbtB=O-DMSO], the first stable oxoborane-Lewis base complex. 6的热解会导致形成相应的氧化物[tbtb = o]。我们还通过热解的1,3,2,4-二甲乙烷纳替烷衍生物的热解，在selenoxoborane [tbtb = se]的产生中成功了。可以根据有关该项目中获得的硼16元素双键化合物的知识来实现2的合成。