peg400介质中铜催化碳杂键偶联反应分析-analysis of copper-catalyzed carbon-heteroatom coupling reaction in peg 400 medium.docxVIP

摘要低分子量聚乙二醇是一种常见的液体低聚物，具有低毒、可生物降解、不挥发、 不可燃、价格低廉等优点，对大多数有机及金属有机化合物溶解性能良好，而且在酸、 碱、高温、O2 和 H2O2 氧化体系以及 NaBH4 还原体系中都很稳定。随着绿色化学发展 的要求，PEG-400 作为一种新型的绿色有机反应溶剂正受到人们的极大关注。本论文研 究了以 PEG-400 为绿色反应介质，铜催化碳-杂键偶联反应研究。首先，我们研究了以 PEG-400 为反应介质，碘化亚铜催化芳基碘、芳基溴与 KOH偶联反应生成芳基酚，获得高达 96%的分离收率。对不同芳基碘和芳基溴进行了考 察，结果表明大部分反应都能得到较高收率。同时，我们还研究了碘化亚铜催化 芳基碘、芳基溴与氨水偶联反应生成芳基胺，获得了高达 96%的分离收率。接着，我们研究了铜催化下芳基碘、芳基溴与 KSCN 或 Na2S·9H2O 发生偶联反 应生成二芳基硫醚，考察了不同芳基卤代烃的电子效应、空间效应和基团的适应性范围，均获得了令人满意的实验结果，获得高达 98%的分离收率。再次，我们研究了铜催化下 2-巯基苯并噻唑与芳基卤的偶联反应，研究发现：利用 不同的铜盐催化可高选择性得到不同的偶联产物。在碘化亚铜催化下、以 KOH 为碱可 高选择性获得 C(aryl)-S 键偶联产物；在氧化铜催化下高选择性获得 C(aryl)-N 键偶联产 物，皆获得高达 95%的选择性和 93%的分离收率。最后，我们研究了在 PEG-400 反应介质中，碘化亚铜催化芳基卤代烃与 Na2Fe(CN)5NO·2H2O 偶联反应生成芳基腈。研究发现芳基碘为底物反应活性较 高，获得高达了 95%的分离收率，而芳基溴在该体系中几乎不反应。关键词： 铜催化，交叉偶联，选择性，PEG-400AbstractLow molecular weight liquid polyethylene glycol (PEG) as a novel green solvent for organic reactions have been attracting great attention. They are non toxic, biodegradable, nonvolatile, nonflammable and inexpensive. Moreover, they can dissolve a great range of organic compounds and organometallic complexes. Thus, PEG-400 as a new reaction medium has begun to attract more attention. The dissertation focuses on copper catalyzed carbon-hetero cross-coupling reactions using PEG-400 as reaction medium.We have developed an efficient CuI/PEG-400 system for hydroxylation of aryl halides with potassium hydroxide. This protocol offers a direct transformation of aryl iodides or bromides to substituted phenols in great diversity with up to 96% isolated yield. Similarly, the cross-coupling reaction between aryl halides with aqueous ammonia was efficiently catalyzed in CuI/PEG-400 system with up to 96% yield.An efficient copper-catalyzed S-arylation of KSCN or Na2S·9H2O with aryl halides in PEG-400 is developed. A range of electron-withdrawing or electron-donating aryl iodides and aryl bromides were found to be applicable to the environmentally benign system. The present procedure is mild and tolerant of a variety of function