Department of Chemistry , Zhejiang University , 866 Yuhangtang Road , Hangzhou 310058 , China.
Org Lett. 2019 Feb 15;21(4):880-884. doi: 10.1021/acs.orglett.8b03299. Epub 2019 Jan 29.
Dual catalyst-controlled intramolecular unactivated C(sp)-H amination and oxygenation of carbamates merging visible-light photocatalysis and earth-abundant transition metal catalysis have been reported. Useful amino alcohol and diol derivatives could be selectively obtained from readily available tertiary alcohol derivatives. The possible mechanisms have been proposed via a 1,5-HAT process followed by Lewis acid-controlled cyclization. The nickel and zinc catalysts inhibit the formation of oxygenation and amination products, respectively. An interesting phenomenon of chirality transfer is also observed.
双催化剂控制的分子内未活化 C(sp)-H 氨化和氧代反应，将可见光光催化和丰富的地球过渡金属催化融合在一起，已经有报道。通过 1,5-HAT 过程和随后的路易斯酸控制的环化反应，可以从易得的叔醇衍生物中选择性地得到有用的氨基醇和二醇衍生物。提出了可能的反应机制。镍和锌催化剂分别抑制了氧代和氨化产物的形成。还观察到了有趣的手性转移现象。
