Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA.
Chem Soc Rev. 2011 Apr;40(4):1870-4. doi: 10.1039/c0cs00165a. Epub 2011 Mar 1.
The functionalization of C-H bonds has yet to achieve widespread use in synthetic chemistry in part because of the lack of synthetic reagents that function in the presence of other functional groups. These problems have been overcome in enzymes, which have metal-oxo active sites that efficiently and selectively cleave C-H bonds. How high-energy metal-oxo transient species can perform such difficult transformations with high fidelity is discussed in this tutorial review. Highlighted are the relationships between redox potentials and metal-oxo basicity on C-H bond activation, as seen in a series of bioinspired manganese-oxo complexes.
C-H 键的功能化在合成化学中尚未得到广泛应用，部分原因是缺乏在其他官能团存在下起作用的合成试剂。这些问题在酶中得到了解决，酶具有金属-氧活性位点，能够有效地、选择性地切割 C-H 键。本综述讨论了高能金属-氧瞬态物种如何以高保真度进行这种困难的转化。强调了在一系列仿生锰氧配合物中观察到的氧化还原电位与 C-H 键活化的金属-氧碱性之间的关系。
