Exploration on Metal-Catalytic Conversion of Sulfinyl Sulfones

Abstract

The utilization of sulfinyl sulfones in transitionmetal-catalyzed synthetic chemistry has rarely been investigated.Here we report the design and utilization of nickel-catalytic conversion of in situ-generated redox-active sulfinyl sulfones for reductive coupling with a wide variety of organic halides by the dual-role nickel catalyst and dual-role reductant Zn. Mechanistic studies disclose that the key design of such a reaction is the employment of redox-active sulfinyl sulfones, enabling the in situ generation of electrophilic sulfur reagents through zinc-induced reduction facilitated by the nickel catalyst. This strategy demonstrates good tolerance for a wide range of organic halides and functional groups. Furthermore, this method extends to meta-substituted functional diaryl sulfides, enabling the modification of complex bioactive molecules and the synthesis of thioether-containing drugs.

Nickel-Catalyzed Reductive Arylation of α-Bromo Sulfoxide

“…To the best of knowledge, the stability of chiral sulfoxides has been seldom tested under reductive conditions. More recently, Zhu, Shao, and their co-workers found sulfinyl sulfones could be reduced to disulfide in the presence of Ni catalysis and Zn . To verify our hypothesis, enantioenriched ( S )-((bromomethyl)sulfinyl)benzene ( S -1a ) was prepared with 98% ee .…”

“…Compared with conventional cross-coupling reactions, these transformations avoid the use of organometallic reagents and bases, high-yielding cross-coupled products with excellent functional group tolerance. To the best of our knowledge, we found that α-bromo sulfoxide has not been used as electrophiles in reductive coupling reactions, probably because the high valent sulfur could be potentially reduced to low valent sulfur under reductive conditions . Driven by the desire for the synthesis of aryl alkyl sulfoxides, herein we report a general and efficient method for the synthesis of functionalized aryl benzyl sulfoxides (Scheme d).…”

Superfast Formation of C(sp2)−N, C(sp2)−P, and C(sp2)−S Vinylic Bonds in Water Microdroplets

“…Furthermore, methods for achieving the analogous C(sp 2 )−S and C(sp 2 )−P bond formations are even less common. While these transformations are known, they require metal catalysts, high temperatures, or long synthetic sequences [18–25] . To the best of our knowledge, no report exists of achieving C(sp 2 )−N, C(sp 2 )−S, and C(sp 2 )−P bond formations via the decarboxylation of vinylic acids.…”

A visible-light-catalyzed sulfonylation reaction of an aryl selenonium salt via an electron donor–acceptor complex

“…There are several methods to synthesize sulfones, and the oxidation of sulfides remains a widely applied strategy, 17–19 which achieves the conversion of intermediate sulfoxide to hydrocarbons with sulfonyl halides catalyzed by a Lewis or Brønsted acid and offers an alternative approach to sulfone synthesis. 20…”