Enantioselective Construction of Chiral Sulfides via Catalytic Electrophilic Azidothiolation and Oxythiolation of N-Allyl Sulfonamides

Abstract

An efficient and convenient pathway was developed for enantioselective synthesis of chiral sulfides by chiral bifunctional selenide-catalyzed electrophilic azidothiolation and oxythiolation of N-allyl sulfonamides. By this protocol, a variety of chiral vicinal azidosulfides and oxysulfides were obtained in good yields with high enantioselectivities and diastereoselectivities. In this transformation, not only electrophilic arylthiolating reagents but also a wide range of electrophilic alkylthiolating reagents worked very well. The practical application of this method was elucidated by further transformations of the products into the diversified compounds.

Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

“…An efficient protocol for intermolecular oxysulfenylation was recently developed by Zhao and co‐workers [29a] . Treatment of N ‐allylsulfonamide 25 with N ‐hexylthiosuccinimide 26 as an electrophilic sulfur source and different oxygen nucleophiles, in the presence of chiral bifunctional selenide catalyst 27 affords a variety of difunctionalized sulfonamides in good yields and high levels of enantioselectivity (Scheme 12).…”

Catalytic Enantioselective Construction of Chiral Benzo-Fused N -Heterocycles through Friedel–Crafts-Type Electrophilic Chlorination

“…Based on previous experience with asymmetric reactions catalyzed by chiral chalcogenides, 49,[63][64][65][66][67][68][69][70][71] we set out to test asymmetric chlorocarbocyclization of N-cinnamyl aniline compound 1 using chiral chalcogenide catalysts in the presence of acid (Table 1). Generally, allyl anilide 1 was easily prepared from the corresponding anilines in two steps.…”

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

“…On the basis of the previous studies,– a plausible reaction pathway is depicted (Scheme ). Firstly, the electrophilic sulfur reagent is activated by catalyst C11 to form intermediate I under the assistance of a Lewis acid.…”