Synthesis of o-Arylenedizinc Compounds and Their Synthetic Applications

邻亚芳基锌化合物的合成及其合成应用

基本信息

批准号：
07640787
负责人：
TAKAGI Kentaro
金额：
$ 1.54万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640787/
关键词：
o-Arylenedizinc Compounds Aryl Triflates o-Bromophenylzinc Compound

项目摘要

Structures of arenes, possessing two different side chains at adjacent positions of benzene ring, are observed in numerous organic compounds. One general way to construct such structures might utilize SE or SN type replacement reaction using synthetic equivalents of o-phenylene dianion, dication, or 1-anion 2-cation as benzo segments with appropriate reagents. In this research, we tried to synthesize o-arylenedizinc compounds, intending to use them as the synthetic equivalent of o-arylene dianion in the synthesis of unsymmetrically 1,2-disubstituted arenes.We have already reported on the synthesis of o-phenylenedizinc compound. However, it appeared that similar route will be less effective for the synthesis of o-arylenedizinc compounds because of the limited availability of 1,2-diiodoarenes. Then, new access to o-arylenedizinc compounds was investigated. That is, regioselective iodination of phenols, followed by triflation of the hydroxyl group, affords aryl triflates containing iodo s … More ubstituent at ortho position. Various o-arylenedizinc compounds were obtained in good yields by the reaction of the aryl triflates with zinc powder.Next, the reaction of o-phenylenedizinc compound with electrophilic reagents was examined. When one equivalent of such reagent as iodobenzene or benzoyl chloride was applied to the reaction in the presence of palladium(0) catalyst containing tris(2,4,6-tri-methoxyphenyl)phosphine or tri(o-tolyl)phosphine as a ligand, formal SE reaction took place selectively at one electrophilic side between two possible centers to afford arylzinc compounds in high yields. Further addition of second reagents to the resulting solutions induce the catalytic reactions once again, providing unsymmetrically 1,2-disubsutituted arenes in good yields.For the first time, o-bromophenylzinc compound as a novel synthetic equivalent of o-phenylene 1-anion 2-cation was prepared by the reaction of o-bromoiodobenzene with zinc powder and was applied to the palladium(0)-catalyzed cross-coupling. Its consecutive treatment with electrophilic reagents like aryl halides or aryl halides and then with nucleophilic reagents like potassium cyanide, alkyne, or arylzinc compounds afforded various unsymmetrically 1,2-disubstituted arenes in good yields. Less

在众多有机化合物中观察到了苯环相邻位置上有两个不同侧链的竞技场的结构。构建此类结构的一种通用方法可以使用o-苯基二角酮，表现或1-Anion 2阵线的合成等效物作为苯并段作为苯并段，并使用适当的试剂。在这项研究中，我们试图合成o-芳二烯酸化合物，打算将它们用作o-芳烃dianion的合成等效物，以综合毫对称器的1,2-脱亚生成剂。但是，由于1,2-二碘烯烯的可用性有限，因此似乎类似的途径对于合成O-芳二烯化合物的有效性较低。然后，研究了对O-氨基化化合物的新访问。也就是说，苯酚的调节碘化，随后是羟基的三裂，提供了含有iodo s的芳基三烯酸盐，在正位位置更含有碘。通过芳基三酯与锌粉的反应，可获得各种O-氨基化化合物。邻苯基二烯基二烯基二烯基化合物与亲电试剂的反应。当在存在含有Tris（2,4,6-三甲氧基）磷酸（2,4,6-三甲氧基）磷酸或Tri（O-Tri基）（O-Tolyl）的磷酸磷酸（O磷酸）正式反应的同时，在一个可能的高中的磷脂催化剂的情况下，将等于碘苯或氯化氯化试剂等效到反应时，将磷酸或Tri（O-Tri基）（O-Tri（O-Tri基）磷酸磷酸置换在一个可能的位置上，则在一个可能的含量下，将磷酸化的高度分配在一个可能的位置上，因此，在一个可能的se基团中，将其置于一个可能的高中。产量。进一步添加第二种试剂到由此产生的溶液中再次诱导催化反应，并以良好的产量为1,2-2-屈服的领域提供。首次，O-溴chomophynylzind化合物是一种新型的合成等效的O-phenylene 1-含量的合成等效，与O-Bromoodobenzene的反应制备了o-Bromoodobenzene的反应。钯（0） - 催化交叉耦合。它连续用芳基卤化物或芳基卤化物等亲电试剂进行治疗，然后用氰化钾，碱或芳基苯基化合物（如核哲学试剂）提供了各种不对称的1,2-二取代的领域。较少的