Atroposelective Sulfenylation of Biaryl Anilines Catalyzed by Chiral SPINOL-Derived Selenide

Abstract

The atroposelective electrophilic sulfenylation of biaryl anilines has been realized for the first time. The reaction is enabled by a new chiral 6,6′-dianisole substituted SPINOL-derived selenide. A variety of axially chiral sulfur-containing biaryl aniline compounds were obtained in moderate to excellent yields with moderate to excellent enantioselectivities. The experimental results suggest that catalyst rigidity is important for the high atroposelectivity.

Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

“…These features make selenium catalysis a highly attractive and useful synthetic tool. In recent years, asymmetric transformations that harness the inherent Lewis basicity of selenium catalysts, including alkene sulfenofunctionalizations, halogenations, and selenoetherifications, have been achieved by the groups of Denmark, Yeung, Zhao, and others . Of particular note, in 2020, Zhao and co-workers utilized a chiral Lewis basic selenide catalyst in the desymmetrizing aromatic chlorination of prochiral arylphosphines to obtain a variety of important acyclic P-stereogenic compounds .…”

Recent advances in selective mono-/dichalcogenation and exclusive dichalcogenation of C(sp2)–H and C(sp3)–H bonds

“…Over the past decade, significant progress has been made in the direct C–H thiolation and selenylation of aromatic rings using various sulfur/selenium sources, such as N -thiosuccinimides, 184,202,203 disulfides/diselenides, 204–210 sulfonyl chlorides, 211,212 sodium sulfinates, 213 thiols, 214–220 sulfonyl hydrazides, 221–223 sulfinamides 224 and thioesters. 225 While sporadic examples of dichalcogenation of electron-rich arenes have been reported, 222,226–230 this section only focuses on some representative examples of selective mono-/dichalcogenation or exclusive dichalcogenation reactions.…”

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

“…Very recently, this strategy was successfully applied to synthesis of axially chiral sulfur-containing biaryl anilines through electrophilic sulfenylation of biaryl anilines by the same group (Scheme 35B). [119] In this work, only a desymmetrization process was involved in the system. In addition to the aforementioned works, Chen's team also reported an antropose-lective electrophilic thiocyanation of indole compounds with N-thiocyanatosaccharin for construction of axially chiral SCN-containing 3-aryl indoles via kinetic resolution approach.…”