SYNTHESIS OF ARYZINC COMPOUNDS AND THEIR APPLICATIONS TO ORGANIC SYNTHESIS

芳基锌化合物的合成及其在有机合成中的应用

基本信息

批准号：
05640667
负责人：
TAKAGI Kentaro
金额：
$ 1.28万
依托单位：
OKAYAMA 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：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05640667/
关键词：
Arylzinc Compound O-Phenylenedizinc Compound Ultrasound 非対称多置換ビフェニル

项目摘要

Organozinc compounds continue to attract synthetic organic chemists to a great extent because if their high chemoselectivity and specific reactivity observed in their further transformations. In this research, we investigated for the first time the direct synthesis of arylzinc compounds from aryl halides and zinc powder promoted by the irradiation of ultrasound. In this method, arylzinc compounds containing electron-withdrawing groups at ortho-positions were obtained readily. The zinc compounds were converted into multi-functional biaryls, which are othewise very difficult to prepare, in high yields by their reaction with aryl halides in the presence of Pd (0)-catalysts.This activation method was also applied to the reaction of o-diiodobenzene with zinc powder, which resulted in the first formation of o-phenylenedizinc compound. After the treatment with chlorotrimethyltin, the zinc compound was identified as the known tin-compound of the corresponding structure. Then, the zinc compound was converted into symmetrical o-terphenyls or 1,2-diacylbenzenes in high yields by the reaction with aryl halides or acyl halides in the presence of Pd (0)-catalyst. Selective monoacylation was also accomplished by the same reaction with acyl halides, except for the use of tris-(2,4,6-trimethoxyphenyl) phosphine in place of other phosphorus ligands in Pd (0) complex.In these studies, we also found the novel displacement of metal ions from organozinc compounds with such nucleophilic reagents as halide ion, thiocyanate ion, or N,N-dialkyldi-thiocarbamate ions by the assistance of NCS.Whereby various organic N,N-dialkyldithio-carbamates or organic thiocyanates were obtained in high yields.

有机锌化合物在很大程度上继续吸引合成有机化学家，因为如果在进一步的转化中观察到它们的高化学选择性和特异性反应性。在这项研究中，我们首次研究了在超声波照射下由芳基卤化物和锌粉直接合成芳基锌化合物。该方法容易获得邻位含有吸电子基团的芳基锌化合物。在 Pd(0)-催化剂存在下，锌化合物通过与芳基卤化物反应，以高产率转化为多官能联芳基化合物，否则很难制备。该活化方法也应用于 o 的反应邻二碘苯与锌粉反应，首先形成邻苯二甲酰亚胺化合物。用氯三甲基锡处理后，该锌化合物被鉴定为相应结构的已知锡化合物。然后，在Pd(0)-催化剂存在下，通过与芳基卤或酰基卤反应，将锌化合物以高收率转化为对称的邻三联苯或1,2-二酰基苯。除了使用三-(2,4,6-三甲氧基苯基)膦代替Pd(0)配合物中的其他磷配体之外，还通过与酰卤进行相同的反应来完成选择性单酰化。在这些研究中，我们还发现借助卤化物离子、硫氰酸根离子或 N,N-二烷基二硫代氨基甲酸根离子等亲核试剂从有机锌化合物中置换金属离子的新方法NCS。由此以高收率获得各种有机N,N-二烷基二硫代氨基甲酸酯或有机硫氰酸酯。