镍催化的酚类Suzuki 偶联反应，由砜基氟甲苯的 SuFEx 实现。

Nickel-Catalyzed Suzuki Coupling of Phenols Enabled by SuFEx of Tosyl Fluoride.

机构信息

School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Rd, Shanghai 200237, China.

出版信息

Molecules. 2023 Jan 7;28(2):636. doi: 10.3390/molecules28020636.

DOI:10.3390/molecules28020636

PMID:36677693

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9864267/

Abstract

A practical and efficient Suzuki coupling of phenols has been developed by using -NiCl(-Tol)(PCy)/2PCy as a catalyst in the presence of tosyl fluoride as an activator. The key for the direct use of phenols lies in the compatibility of the nickel catalyst with tosyl fluoride (TsF) and its sulfur(VI) fluoride exchange (SuFEx) with C-OH. Water has been found to improve the one-pot process remarkably. The steric and electronic effects and the functional group compatibility of the one-pot Suzuki coupling of phenols appear to be comparable to the conventional one of pre-prepared aryl tosylates. A series of electronically and sterically various biaryls could be obtained in good to excellent yields by using 3-10 mol% loading of the nickel catalyst. The applications of this one-pot procedure in chemoselective derivatization of complex molecules have been demonstrated in 3-phenylation of estradiol and estrone.

摘要

已开发出一种实用且高效的酚类铃木偶联反应方法，即在砜氟作为活化剂的存在下，使用 -NiCl(-Tol)(PCy)/2PCy 作为催化剂。直接使用酚类物质的关键在于镍催化剂与砜氟（TsF）的相容性，以及其与 C-OH 的硫（VI）氟化物交换（SuFEx）。现已发现水可显著改善一锅法工艺。酚类物质的铃木偶联一锅法的空间位阻和电子效应以及官能团兼容性似乎与预制备的芳基对甲苯磺酸盐的常规一锅法相当。使用 3-10mol%负载量的镍催化剂，可以以良好至优异的收率得到一系列电子和空间位阻不同的联芳烃。该一锅法在复杂分子的选择性衍生化中的应用已在雌二醇和雌酮的 3-芳基化中得到证明。