Iodine-catalyzed Sulfonylation of Arylacetylenic Acids and Arylacetylenes with Sodium Sulfinates: Synthesis of Arylacetylenic Sulfones

Abstract

A highly efficient and generally applicable iodine-catalyzed reaction of arylacetylenic acids and arylacetylenes with sodium sulfinates for the synthesis of arylacetylenic sulfones was developed. The methodology has the advantages of a metal-free strategy, easy to handle reagents, functional group tolerance, a wide range of arylacetylenic acids and arylacetylenes, and easy access to arylacetylenic sulfones.

Iodide/tert‐Butyl Hydroperoxide‐Mediated Benzylic C–H Sulfonylation and Peroxidation of Phenol Derivatives

“…of TEMPO (2,2,6,6‐tetratmethyl‐1‐piperidinyloxy) to test the reaction pathway, and the sulfonylation and peroxidation were completely suppressed. On the basis of the above results and related reports,,– we propose a tentative mechanism for the benzylic C–H sulfonylation and peroxidation. As illustrated in Scheme , initially, t‐ BuO radical and t‐ BuOO radical are generated.…”

Metal‐Free Iodosulfonylation of Internal Alkynes: Stereodefined Access to Tetrasubstituted Olefins

“…Finally, based on the literature precedents,,,– and our control experiments we predicted a mechanism as shown in Scheme . The overall process can be considered in three steps.…”

Mono‐ and Bimetallic Alkynyl Metallocenes and Half‐Sandwich Complexes: A Simple and Versatile Synthetic Approach

“…[15] Based on these results, we envisioned the possibility of using lithium metallocenesi nr eactions with arylsulfonylacetylenes (commercially available or easily prepared in one step from alkynes [16] )a sageneral method foro btaining the coupling of alkynyl and metallocenyl moieties (Scheme 1, equation c). [15] Based on these results, we envisioned the possibility of using lithium metallocenesi nr eactions with arylsulfonylacetylenes (commercially available or easily prepared in one step from alkynes [16] )a sageneral method foro btaining the coupling of alkynyl and metallocenyl moieties (Scheme 1, equation c).…”

“…Recently,w ehave reportedt he electrophilic behavior of arylsulfonylacetylenes with organolithium reagents through an unusual a-attack( anti-Michael addition) followed by elimination of the ArSO 2 moiety to allow the alkynylation of lithiated sp 2 and sp 3 carbon atoms, yielding the corresponding alkynes. [15] Based on these results, we envisioned the possibility of using lithium metallocenesi nr eactions with arylsulfonylacetylenes (commercially available or easily prepared in one step from alkynes [16] )a sageneral method foro btaining the coupling of alkynyl and metallocenyl moieties (Scheme 1, equation c). In this work, we presentt he results obtained in this research which has provided differenta lkynyl metallocenes,h alf-sandwich derivatives, and bis-metallocenyl alkynes.T he clear advantages of our procedure with respectt ot hose so far reported, concerning experimental simplicity,c onditions and yields determine our reaction must be considered as the method of choice for preparing these important class of compounds.…”