Yang Jun, Ji Ding-Wei, Hu Yan-Cheng, Min Xiang-Ting, Zhou Xiangge, Chen Qing-An
Institute of Homogeneous Catalysis , College of Chemistry , Sichuan University , Chengdu 610064 , P. R. China . Email:
Dalian Institute of Chemical Physics , Chinese Academy of Sciences , Dalian 116023 , P. R. China . Email:
Chem Sci. 2019 Aug 26;10(41):9560-9564. doi: 10.1039/c9sc03747k. eCollection 2019 Nov 7.
Terpenes, consisting of isoprene monomer units, represent a family of naturally abundant compounds. The difunctionalization of terpenes is highly appealing yet remains challenging, since the multiple unbiased C[double bond, length as m-dash]C bonds of terpenes lead to difficulty in controlling the regioselectivity. Herein, a cobalt(iii)-catalyzed C-H activation strategy has been developed to facilitate hydroxymethylarylation of terpenes with formaldehyde and arenes with high chemo- and regio-selectivities. These (chemo- and regio-) selectivities are governed by the coordination abilities of isoprene, directing groups and the steric effect. This terpene difunctionalization also features high atom and step economy through a C-H addition pathway.
萜类化合物由异戊二烯单体单元组成,是一类天然丰富的化合物。萜类化合物的双官能团化极具吸引力,但仍具有挑战性,因为萜类化合物中多个无偏向的碳-碳双键导致区域选择性控制困难。在此,已开发出一种钴(III)催化的C-H活化策略,以促进萜类化合物与甲醛和芳烃的羟甲基芳基化反应,具有高化学选择性和区域选择性。这些(化学和区域)选择性受异戊二烯、导向基团的配位能力和空间效应的控制。这种萜类化合物的双官能团化还通过C-H加成途径具有高原子经济性和步骤经济性。