使用机械化学生成的钙基重格氏试剂(R-Ca X)对有机卤化物进行直接硼化  

Direct Borylation of Organohalides Using Mechanochemically Generated Calcium-Based Heavy Grignard Reagents(R-CaX)

作　　者：刘雨涵 高盼 Liu Yuhan;Gao Pan(College of Chemistry and Chemical Engineering,Yangzhou University,Yangzhou 225002,China)

机构地区：[1]扬州大学化学化工学院,扬州225002

出　　处：《化学学报》2024年第11期1114-1119,共6页Acta Chimica Sinica

基　　金：中国博士后科学基金(No.2021M692713);江苏省自然科学基金(No.BK20210789)资助。

摘　　要：钙基重格氏试剂(R-CaX)的研究由于其合成难度大,至今应用较少.钙基重格氏试剂相较于镁基格氏试剂(R-MgX)而言,碳金属键具备更强的极性和离子化特性,因此可以在某些转化中表现出独特的反应活性.传统合成钙基重格氏试剂需对金属钙进行预先活化,例如使用有毒的液氨或者高活性的金属锂,这些苛刻的反应条件严重阻碍了其在实验室和工业生产中的应用.本研究利用球磨机产生的持续的机械能破坏金属钙表面的惰性氧化层,实现钙的原位活化,随后直接插入卤代烃的碳卤键,原位生成相应的钙基重格氏试剂.随后,R-CaX作为碳亲核试剂与频哪醇硼烷(HBpin)反应,成功合成了有机硼化合物,并具有良好的底物兼容性;特别是在使用难溶溴代芳烃作为底物时,该机械化学方法与传统溶液反应体系相比,展现出独特的优势.The study of calcium-based Grignard reagents(R-CaX)has historically been limited due to the challenges in their synthesis.However,calcium's biocompatibility and distinct chemical properties make it a highly promising candidate for organic synthesis applications.Unlike their magnesium-based counterparts(R-MgX),calcium-based reagents exhibit stronger polarity and a higher degree of ionic character in the carbon-metal bond.This increased ionic nature can result in unique reactivity,offering advantages in specific transformations where magnesium-based reagents may be less effective.Traditional methods for synthesizing calcium-based Grignard reagents are cumbersome,requiring the pre-activation of metallic calcium through processes involving toxic materials such as liquid ammonia or highly reactive lithium.These harsh conditions not only present safety concerns but also limit the reagents'practicality,particularly in industrial applications where scalability and safety are crucial.In recent years,mechanochemistry has emerged as a sustainable alternative to conventional methods,providing opportunities to improve reaction efficiency and reduce the use of solvents.The mechanical energy generated by ball milling has been shown to disrupt the inert surface layer of metallic calcium,allowing for in situ activation.This enables the calcium to react with organohalides,forming calcium-based Grignard reagents without the need for toxic reagents or complex pre-activation steps.Once formed,these reagents can act as carbon nucleophiles,reacting with pinacolborane(HBpin)to form organoboron compounds,which are valuable intermediates in organic synthesis.This study demonstrates that by utilizing the continuous mechanical energy of ball milling,a variety of boronated products can be synthesized efficiently and with high yields.The method also shows broad substrate compatibility,particularly excelling in reactions involving poorly soluble aryl bromides,where traditional solution-based systems often fail.In conclusion,this work marks the

关 键 词：钙基重格氏试剂 机械化学 硼化反应 绿色化学 无溶剂 

分 类 号：O62[理学—有机化学]