Simple and Efficient Synthesis of Allyl Sulfones through Cs2CO3-Mediated Radical Sulfonylation of Morita–Baylis–Hillman Adducts with Thiosulfonates

Abstract

A highly efficient and eco-friendly method has been developed for the synthesis of allyl sulfones using Morita-Baylis-Hillman (MBH) adducts and thiosulfonates under mild conditions. The Cs2CO3-promoted radical sulfonylation provided a series of allyl sulfones in good to high yields with high stereoselectivities. A wide variety of MBH bromides/acetates as well as thiosulfonates were tolerated and reliable in scale-up synthesis. A plausible mechanism was also proposed to rationalize the radical sulfonylation of the experimental outcome and control experiments.

Photoinduced Alkylsulfonylation and Cyanoalkylsulfonylation of Morita–Baylis–Hillman Adducts via Multicomponent Insertion of Sulfur Dioxide

“…A great deal of radical donors, such as Langlois’ reagent, N -hydroxyphthalimide esters (NHPI esters), potassium organotrifluoroborates, tertiary amines, ethers, α-bromo ketones, or NHC-boranes have been proved to be ideal C or B-radical precursors under photoredox catalysis or electrocatalysis to provide numerous trisubstituted olefins (Scheme a). In addition, the aryl sulfonylation of MBH adducts has been identified as an efficient method to obtain allylic sulfones by exploiting various sulfonyl reactants . For instance, Li and co-workers reported TBAI-catalyzed aryl sulfonylation of MBH adducts with sulfonylhydrazides by utilizing TBHP as oxidation agents .…”

The Synthesis of (E)‐Vinyl and Alkynyl Sulfones by the Formation of an Electron Donor‐Acceptor Complex Using Thiosulfonates and Sodium Iodide Under Visible Light

“…As a sulfur‐containing reagent, thiosulfonate is characterized by being odorless and environmentally friendly, which has attracted the attention of many chemists [30–49] . Therefore, a variety of methods for cracking thiosulfonates into active species have been developed as shown in Scheme 1a, (1), [35] (2), [38,50,51] (3), [31,50,52,53] (4), [32,36,37,40,54–57] leading to various methods for construction of C−S bonds. Despite the significance of these approaches, there are still plagued by at least one of the following limitations: (1) the use of transition metal catalysts, (2) the need for high reaction temperature, (3) the necessity of photocatalysts and, (4) hyperoxides as oxidants.…”

Regiodivergent sulfonylation of terminal olefins via dearomative rearrangement

“…[11][12][13] Alternatively, the stoichiometric oxidation 14 of sulfides with strong oxidants has also provided allylsulfones. 1 Other alternatives from alkenes include metal catalyzed (e.g., Pd 7,15,16 & Cu 17 ) and substitutions [18][19][20] reactions. Couplings of allylic alcohols with sulfinyl chlorides, 21 activated by NBS, 22 or catalyzed by Pd 3,23 have afforded allylsulfone.…”

“…1 Other alternatives from alkenes include metal catalyzed ( e.g. , Pd 7,15,16 & Cu 17 ) and substitutions 18–20 reactions. Couplings of allylic alcohols with sulfinyl chlorides, 21 activated by NBS, 22 or catalyzed by Pd 3,23 have afforded allylsulfone.…”