Nonbasic Synthesis of Thioethers via Nickel-Catalyzed Reductive Thiolation Utilizing NBS-Like N-Thioimides as Electrophilic Sulfur Donors

Abstract

The nonbasic synthesis of unsymmetrical thioethers via nickel-catalyzed reductive thiolation between aryl(hetero) iodides and N-thioimides is illustrated. N-Bromosuccinimide (NBS)-like Nthioimides were found quite reactive toward thiolation with carbon electrophiles, and a series of structurally varied thioethers were successfully prepared under mild reaction conditions. The transformation was featured with the new application of the NBS-like reagents, good functional group tolerance, and late-stage modification of biologically active scaffolds, thus providing an expeditious and efficient platform to construct polyfunctional thioethers.

Copper-Catalyzed Chemoselective Coupling of N-Dithiophthalimides and Alkyl Halides: Synthesis of Unsymmetrical Disulfides and Sulfides

“…On the basis of the results presented above and literature reports, we propose a plausible reaction mechanism as shown in Scheme . First, Cu I A undergoes oxidative addition with Harpp reagent 1 to form intermediate B , and then phthalimide ions leave and regenerate Cu I C in the presence of a reductant.…”

Research Progress in C—S Coupling Reactions of Aryl Halides

“…反应条件筛选发现以 NiCl 2 (PPh 3 ) 2 为催化剂, 1,10-菲罗 啉为配体, 锌为还原剂的反应体系效率极高, 模型反应 能够获得大于 99%收率的硫醚. 该反应以 DMF 为溶剂, 2023 年, 该课题组 [78] 在继续优化反应条件时 发现 NiBr 2 也能有效催化该反应进行. 图式 65 以硫代乙酸钾为硫源合成二芳基硫醚 Scheme 65 Synthesis of diaryl sulfide using potassium thioacetate as sulfur source 2022 年, Hopkins 课题组 [84] 采用 t-BuBrettPhos Pd G3 新型催化剂用于芳基卤化物与硫代乙酸酯的硫醚化 反应(Scheme 66).…”

Selective nickel-catalyzed disulfuration of alkyl halides with di/trithiosulfonates

“…By contrast, the use of electrophilic sulfurating reagents to access sulfur-containing compounds via nickel-catalyzed cross-electrophile coupling 14 has received increasing attention and is considered a useful strategy. Based on the findings of previous studies for reductive monosulfuration, 15–17 recently the Wang and Ackermann group discovered that tetrasulfides as double sulfur (–SS–) transfer precursors could be successfully applied in a simple nickel-catalyzed cross-electrophilic coupling to access disulfuration products, with alkyl radical and Ni I /Ni III species proposed to be involved (Scheme 1IC). 18 Despite the aforementioned progress, compared to well-established monothiosulfonate reagents for metal-catalyzed conversions, nickel-catalytic reductive coupling of electrophilic di/trithiosulfonates is apparently much less developed, and the activation modes are also unclear, probably due to the challenging activation of multiple S–S bonds.…”