Ruthenium(II)-Catalyzed Regioselective Ortho C-H Allenylation of Electron-Rich Aniline and Phenol Derivatives
Ruthenium(II)-Catalyzed Regioselective Ortho C-H Allenylation of Electron-Rich Aniline and Phenol Derivatives
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钌(II)催化富电子苯胺和苯酚衍生物的区域选择性邻位C-H烯酰化
DOI：
10.1021/acs.joc.9b02787
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发表时间：
2020
影响因子：
3.6
通讯作者：
Zhou Bing
中科院分区：
文献类型：
--
作者：
Chen Yanni;Hu Liuyu;Liang Liuchun;Guo Fujiang;Yang Yaxi;Zhou Bing
富电子苯衍生物与丙炔醇衍生物的邻羟基丙烯化一直是一个挑战，因为它们天生倾向于通过SN2 '型取代过程发生对羟基丙烯化。在这里，我们描述了Ru（II）催化的富电子苯胺和苯酚衍生物的区域选择性邻位C-H烯化反应，这使得以前具有挑战性的广泛邻位烯化苯胺和苯酚衍生物的合成成为可能。更重要的是，高光学活性的完全取代的烯也可以通过高效手性转移制备具有高对映体过量的烯。在目前的催化体系中没有观察到对C-H烯化产物，因此显示出完全的区域选择性可逆性。
Ortho C–H allenylation of electron-rich benzene derivatives with propargylic alcohol derivatives has been a challenge, due to their great innate tendency toward a para C–H allenylation via an SN2′-type substitution process. Here, we described a Ru(II)-catalyzed regioselective ortho C–H allenylation of electron-rich aniline and phenol derivatives, which allows the previously challenging synthesis of a broad range of ortho allenylated aniline and phenol derivatives. More significantly, highly optically active fully substituted allenes can also be prepared with high enantiomeric excess via a highly efficient chirality transfer. No para C–H allenylation product was observed in the current catalytic system, thus showing a complete reversibility of the regioselectivity.