Well‐Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides

Abstract

Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation of aryl and heteroaryl bromides were investigated.

Palladium‐Catalyzed 2,2,2‐Trifluoroethoxylation of Aromatic and Heteroaromatic Chlorides Utilizing Borate Salt and the Synthesis of a Trifluoro Analogue of Sildenafil

“…To overcome the difficulties of classical ether syntheses, many efforts have been made recently towards the 2,2,2‐trifluoroethoxylation of aryl‐halides by copper‐catalyzed reactions, granting a new approach to trifluoroethyl‐aryl ethers. Weng and co‐workers developed a copper‐mediated procedure for the transformation of various (hetero)aryl bromides to the corresponding trifluoroethyl ether, with good functional‐group tolerance. However, the reaction requires stoichiometric amounts of a copper–organic reagent and the addition of strong base.…”

Recent Advances of Direct Incorporation of Fluorine-Containing Groups and 18F-Labeling Methods

“…图式 33 2H-氮丙啶的合成以及其可能的机理 Scheme 33 Synthesis of 2H-azirines and its proposed mechanism 最近, 翁志强课题组在之前[(bpy)Cu(SCF 3 )] [63] 以及 [(bpy)Cu(SeCF 3 )] 2 [81] 的 研 究 基 础 上 , 继 续 探 索 并 报 道 [88,90] 在钯催化下, 芳基溴代物以及溴代查尔酮可以与三 氟乙醇进行三氟乙氧基化反应得到 CF 3 CF 2 O 基团连接 在 芳 环 上 的 产 物 [92] (Scheme 36). 该 反 应 用 到 的 Pd/t-BuXPhos 或者 Pd/JohnPhos 配体催化体系可以促进 三氟乙醇与芳基溴化物以及溴代查尔酮的交叉偶合反 应, 但是对富电子的芳香体系没有作用.…”

Cobalt-catalyzed peri-selective alkoxylation of 1-naphthylamine derivatives

“…In particular, the formation of C–O bonds is widely used in the syntheses of pharmaceuticals and functional materials [14–17]. The direct hydroxylation [18–19] and acetoxylation [20–22] have been developed rapidly in recent years.…”

“…Over the past few decades, transition-metal-catalyzed C–H activation to form C–C or C–heteroatom bonds has attracted more attention [ 8 – 13 ]. In particular, the formation of C–O bonds is widely used in the syntheses of pharmaceuticals and functional materials [ 14 – 17 ]. The direct hydroxylation [ 18 – 19 ] and acetoxylation [ 20 – 22 ] have been developed rapidly in recent years.…”