Ligand-Controlled Divergent Cross-Coupling Involving Organosilicon Compounds for Thioether and Thioester Synthesis

Abstract

A divergent cross-coupling for both thioether and thioester construction from organosilicon compounds has been developed. Predominant selectivity for Hiyama-type coupling and C1 insertion reaction was achieved under the guidance of ligands. Thioether was obtained under ligand-free conditions in which disulfide generated from homocoupling could be prevented. Meanwhile, application of bidentate phosphine ligands under carbon monoxide atmosphere (CO balloon) afforded the thioester with little decomposition, which was revealed through interval NMR tracking.

Metal‐Catalyzed Synthesis and Use of Thioesters: Recent Developments

“…In 2016, Jiang et al. developed a carbonylative Hiyama‐type cross‐coupling between thiosulfate 22 and the organosilicon reagent 23 catalyzed by PdCl 2 ⋅dppp (5 mol %) with additional ligand L3 and only 1 atm of CO (Scheme ) . CuF 2 served both as oxidant and fluoride source.…”

“…In 2016, Jiang et al developed ac arbonylative Hiyama-type cross-coupling between thiosulfate 22 and the organosiliconr eagent 23 catalyzed by PdCl 2 ·dppp (5 mol %) with additional ligand L3 and only 1atm of CO (Scheme 11). [29] CuF 2 served both as oxidant Scheme8.First thiocarbonylationo faryl iodides reported by Alper et al [23] Scheme9.Thiocarbonylation of aryl iodides using aC Os urrogate reported by Skrydstrup et al [25] DPEphos:bis[(2-diphenylphosphino)phenyl]e ther.…”

“…Carbonylative cross-coupling of thiosulfates 22 and organosilicon compounds 20. [29] dppm:1,1-bis(diphenylphosphino)methane. DMA:d imethylacetamide.…”

Furfuryl Cation Induced Three‐Component Reaction to Synthesize Triazole‐Substituted Thioesters

“…Jiang and co‐workers reported a Pd‐catalyzed CO insertion cross‐coupling between organosilicon compounds and thiosulfates, that represented an odorless thioesterification method. [17a] An elegant transition‐metal‐free synthesis of an α‐ketothioester via the three‐component reaction of an α‐hydroxyl ketone, elemental sulfur and a benzyl halide was developed by the same group. [17b] Nonetheless, several limitations have been observed in some approaches including the use of highly reactive oxidants, expensive metal catalysts, long reaction times, harsh reaction conditions, and others ,.…”

“…[17a] An elegant transition‐metal‐free synthesis of an α‐ketothioester via the three‐component reaction of an α‐hydroxyl ketone, elemental sulfur and a benzyl halide was developed by the same group. [17b] Nonetheless, several limitations have been observed in some approaches including the use of highly reactive oxidants, expensive metal catalysts, long reaction times, harsh reaction conditions, and others ,. [14e] So, the thioesterification reactions under metal‐free conditions have attracted the attention of chemists,, [11h], [13g] because they are desired particularly in the pharmaceutical synthesis.…”