Visible-Light-Induced Chemoselective Synthesis of α-Chloro and Vinyl Sulfones by Sulfonylation of Alkenes

Abstract

Direct sulfonylation between alkenes and sulfonyl chloride was achieved at room temperature by a visible-light-induced photo­redox process. This method allows the chemoselective synthesis of α-chloro and vinyl sulfone derivatives with moderate to high yields. The selectivity of the reaction was fully controlled by the electronic properties of the alkenes.

Visible Light as the Key for the Formation of Carbon–Sulfur Bonds in Sulfones, Thioethers, and Sulfonamides: An Update

“…Also, in 2018, Kim and Han reported the same chlorosulfonylation observed by Niu and Ni for electron-rich alkenes 40 but employing internal and terminal arylacetylenes as coupling partners. 41 Notably, both aliphatic and aromatic sulfonyl chlorides yielded the desired product.…”

“…In 2018, Niu examined these two possibilities reporting a chemo-selective synthesis of αchloro sulfone 69a and vinyl sulfone derivatives 69b. 39 The author reacts arylsulfonylchlorides 57 with alkenes 68a and 68b in the presence of Ru(bpy)3Cl2•6H2O as the photocatalyst under blue light irradiation. Interestingly, they demonstrated that electrondonating substituents on the alkenes 68b direct the reactivity towards the formation of vinyl sulfones 69b whereas electronwithdrawing groups yielded β-chloro sulfones 69a (Scheme 27).…”

Novel Convenient Approach to 6-, 7-, and 8-Numbered Nitrogen Heterocycles Incorporating Endocyclic Sulfonamide Fragment

“…Much to our surprise, this methodology was never applied to unsaturated compounds with double or triple carbon-carbon bond as nucleophilic site and sulfonyl chloride as electrophile. Although intermolecular addition of sulfonyl chlorides to olefins under free-radical conditions (atom transfer radical addition) is well documented and widely used for the preparation of α-chloro sulfones and vinyl sulfones (see e.g., [ 25 , 26 , 27 , 28 , 29 ] and references therein), there is only one publication reporting small-scale homolytic intramolecular heterocyclization of pent-4-sulfonyl chloride proceeding at high temperature (AIBN-CuCl 2 , MeCN, 170 °C) and resulting in 3-chlorotetrahydrothiopyran 1,1-dioxide in a low yield (17%) [ 30 ]. Obviously, this heterocyclization is of low preparative value and has rather theoretical meaning.…”

Recent Progress in Sulfonylation via Radical Reaction with Sodium Sulfinates, Sulfinic Acids, Sulfonyl Chlorides or Sulfonyl Hydrazides

“…In 2018, Ni group found that different products were isolated from the visible light induced sulfonylation reaction of alkenes and sulfonyl chloride [90] . The selectivity of the reaction was fully controlled by the electronic properties of the alkenes.…”