Department of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
ICREA, Pg. Lluís Companys 23, 08010, Barcelona, Spain.
Angew Chem Int Ed Engl. 2018 Mar 26;57(14):3825-3829. doi: 10.1002/anie.201712725. Epub 2018 Mar 1.
The transformation of C-H bonds into more reactive C-M bonds amenable to further functionalization is of fundamental importance in synthetic chemistry. We demonstrate here that the transformation of neutral bismuth compounds into their cationic analogues can be used as a strategy to facilitate CH activation reactions. In particular, the double CH activation of bismuth-bound diphenyl amide, (NPh ) , is reported along with simple one-pot procedures for the functionalization of the activated positions. The organometallic products of the first and second CH activation steps were isolated in high yields. Analysis by NMR spectroscopy, single-crystal X-ray diffraction, and DFT calculations revealed unusual ground-state properties (e.g., ring strain, moderate heteroaromaticity), and provided mechanistic insight into the formation of these compounds.
C-H 键转化为更具反应性的 C-M 键，从而进一步官能化，这在合成化学中具有重要意义。我们在这里证明，将中性铋化合物转化为其阳离子类似物可以用作促进 CH 活化反应的策略。特别是，报道了双 CH 活化铋键联二苯甲酰胺（NPh ），以及用于活化位置官能化的简单一锅法程序。第一和第二 CH 活化步骤的有机金属产物以高产率分离。通过 NMR 光谱、单晶 X 射线衍射和 DFT 计算分析揭示了其不寻常的基态性质（例如，环应变、适度的杂芳性），并为这些化合物的形成提供了机理见解。
