Evolution of C-H Bond Functionalization from Methane to Methodology.
Evolution of C-H Bond Functionalization from Methane to Methodology.
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DOI：
10.1021/jacs.5b08707
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发表时间：
2016-01-13
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Hartwig JF
该观点介绍了基本原理，基元反应，初始催化体系和当代催化剂，这些催化剂将C-H键官能化从好奇心转变为合成化学家的现实。许多类涉及过渡金属配合物的基元反应在典型的非反应性位置裂解C-H键。这些反应，再加上一个单独或同时的官能化过程，导致含有新的C-C，C-N和C-O键的产物。这种反应最初被研究用于将轻质烷烃转化为液体产物，但它们最常用于（在某些情况下商业化）合成更复杂结构的天然产物、药用活性化合物和芳香族材料。C-H键官能化研究方向的这种变化是显著的，因为反应必须发生在未活化的C-H键上，而官能团对经典试剂的反应性比C-H键更强。将介绍形成C-C键或在未活化的C-H键上安装功能的反应的范围，并将讨论这些反应的潜在未来用途。
This Perspective presents the fundamental principles, the elementary reactions, the initial catalytic systems, and the contemporary catalysts that have converted C−H bond functionalization from a curiosity to a reality for synthetic chemists. Many classes of elementary reactions involving transition-metal complexes cleave C−H bonds at typically unreactive positions. These reactions, coupled with a separate or simultaneous functionalization process lead to products containing new C−C, C−N, and C−O bonds. Such reactions were initially studied for the conversion of light alkanes to liquid products, but they have been used (and commercialized in some cases) most often for the synthesis of the more complex structures of natural products, medicinally active compounds, and aromatic materials. Such a change in direction of research in C−H bond functionalization is remarkable because the reactions must occur at an unactivated C−H bond over functional groups that are more reactive than the C−H bond toward classical reagents. The scope of reactions that form C−C bonds or install functionality at an unactivated C−H bond will be presented, and the potential future utility of these reactions will be discussed.