Nickel‐Catalyzed Sulfonylation of C(sp²)–H Bonds with Sodium Sulfinates

Abstract

The first nickel‐catalyzed ortho‐sulfonylation of C(sp2)–H bonds with sodium sulfinates directed by (pyridin‐2‐yl)isopropylamine (PIP‐amine) is described. This strategy exhibits a broad substrate scope and good functional group tolerance with high monosulfonylation selectivity. Besides arenes and heteroarenes, the reaction can also be extended to alkenes, providing diverse diaryl and alkyl aryl sulfones in high yields. Furthermore, a plausible Ni(I)/Ni(III) mechanism is outlined based on our experimental results and related precedents.magnified image

Oxidative Sulfonylation of Multiple Carbon‐Carbon bonds with Sulfonyl Hydrazides, Sulfinic Acids and their Salts

“…Besides copper, the NiBr 2 /Ag 2 CO 3 /PhCOOH system in chloroform at 120 °C was also applied for o ‐sulfonylation of PIP‐substituted benzamides with sodium sulfinates. In this case, sulfones were obtained in 20–90% yields, and sometimes sulfonylation of two o ‐positions was observed [173] …”

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds

“…Similarly, in 2017, Gong, Song, and co-workers developed a Ni-catalyzed ortho-sulfonylation of C(sp2)-H bonds with sodium sulnates directed by (pyridin-2-yl)isopropylamine (Table 17B). 261 Various diaryl and alkyl aryl sulfones were prepared in 20-90% yields under the catalytic inuence of NiBr 2 (10 mol%) with Ag 2 CO 3 (2.0 equiv.) as an oxidant in CHCl 3 at 120 C. In addition to arene and heteroarene substrates, the method can also be applied to alkene substrates to provide the desired vinyl sulfones.…”

Tetrabutylammonium Iodide Mediated Sulfenylation of Poly­substituted 1H-Pyrazol-5-amines with Arylsulfonyl Hydrazides

“…37 Next, the sulfenylation of 1a can proceed through two different routes; route 1: 1a and 2aa undergo a nucleophilic substitution reaction to give the intermediate III and p-tolylsulfinic acid. Next, p-tolylsulfinic acid promotes removal the Ts group of III to provide final product 3a and benzenesulfinic benzenesulfonic anhydride (IV); 38 route 2: 1a removes the Ts group to afford the intermediates 4a and IV. Subsequently, 4a undergoes electrophilic substitution with 2aa to give the product 3a.…”