Chen Herong, Zhou Zhijun, Kong Wangqing
The Institute for Advanced Studies (IAS), Wuhan University Wuhan Hubei 430072 P. R. China
Chem Sci. 2021 Jun 7;12(27):9372-9378. doi: 10.1039/d1sc02625a. eCollection 2021 Jul 14.
Methanol is an abundant and renewable chemical raw material, but its use as a C1 source in C-C bond coupling reactions still constitutes a big challenge, and the known methods are limited to the use of expensive and noble metal catalysts such as Ru, Rh and Ir. We herein report nickel-catalyzed direct coupling of alkynes and methanol, providing direct access to valuable allylic alcohols in good yields and excellent chemo- and regioselectivity. The approach features a broad substrate scope and high atom-, step- and redox-economy. Moreover, this method was successfully extended to the synthesis of [5,6]-bicyclic hemiacetals through a cascade cyclization reaction of alkynones and methanol.
甲醇是一种丰富的可再生化学原料，但其在碳-碳键偶联反应中作为C1源的应用仍然是一个巨大的挑战，并且已知的方法仅限于使用诸如钌、铑和铱等昂贵的贵金属催化剂。我们在此报告了镍催化的炔烃与甲醇的直接偶联反应，能够以良好的产率以及出色的化学和区域选择性直接合成有价值的烯丙醇。该方法具有广泛的底物范围以及高原子经济性、步骤经济性和氧化还原经济性。此外，通过炔酮与甲醇的串联环化反应，该方法成功扩展至[5,6]-双环半缩醛的合成。
