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      Iodine catalyzed cross-dehydrogenative C–S coupling by C(sp2)–H bond activation: direct access to aryl sulfides from aryl thiols

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          Abstract

          An efficient, simple and facile green protocol for the direct sulfenylation of electron-rich species from readily available aryl thiols with the aid of molecular iodine under solvent-free, metal-free and aerobic conditions provides a variety of aryl sulfides in excellent yields.

          Abstract

          A novel, efficient and unprecedented green protocol for the formation of C–S bonds has been developed under metal-free conditions. This protocol involves the synthesis of aryl sulfides through the cross-dehydrogenative coupling of readily available aryl thiols with electron-rich species under solvent-free conditions and the corresponding aryl sulfides are obtained in high to quantitative yields. A catalytic amount of inexpensive and non-toxic iodine drives the reaction and no exclusion of air and expensive ligands is required.

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          Most cited references75

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          Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds.

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            Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations.

            Synthetic chemists aspire both to develop novel chemical reactions and to improve reaction conditions to maximize resource efficiency, energy efficiency, product selectivity, operational simplicity, and environmental health and safety. Carbon-carbon bond formation is a central part of many chemical syntheses, and innovations in these types of reactions will profoundly improve overall synthetic efficiency. This Account describes our work over the past several years to form carbon-carbon bonds directly from two different C-H bonds under oxidative conditions, cross-dehydrogenative coupling (CDC). We have focused most of our efforts on carbon-carbon bonds formed via the functionalization of sp(3) C-H bonds with other C-H bonds. In the presence of simple and cheap catalysts such as copper and iron salts and oxidants such as hydrogen peroxide, dioxygen, tert-butylhydroperoxide, and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), we can directly functionalize various sp(3) C-H bonds by other C-H bonds without requiring preactivation. We demonstrate (1) reaction of alpha-C-H bonds of nitrogen in amines, (2) reaction of alpha-C-H bonds of oxygen in ethers, (3) reaction of allylic and benzylic C-H bonds, and (4) reaction of alkane C-H bonds. These CDC reactions can tolerate a variety of functional groups, and some can occur under aqueous conditions. Depending on the specific transformation, we propose the in situ generation of different intermediates. These methods provide an alternative to the separate steps of prefunctionalization and defunctionalization that have traditionally been part of synthetic design. As a result, these methods will increase synthetic efficiencies at the most fundamental level. On an intellectual level, the development of C-C bond formations based on the reaction of only C-H bonds (possibly in water) challenges us to rethink some of the most fundamental concepts and theories regarding chemical reactivities. A successful reaction requires the conventionally and theoretically less reactive C-H bonds to react selectively in the presence of a variety of functional groups. With further investigation, we expect that C-C bond formations based on cross-dehydrogenative coupling will have a positive economic and ecological impact on the next generation of chemical syntheses.
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              The atom economy--a search for synthetic efficiency.

              B M Trost (1991)
              Efficient synthetic methods required to assemble complex molecular arrays include reactions that are both selective (chemo-, regio-, diastereo-, and enantio-) and economical in atom count (maximum number of atoms of reactants appearing in the products). Methods that involve simply combining two or more building blocks with any other reactant needed only catalytically constitute the highest degree of atom economy. Transition metal-catalyzed methods that are both selective and economical for formation of cyclic structures, of great interest for biological purposes, represent an important starting point for this long-term goal. The limited availability of raw materials, combined with environmental concerns, require the highlighting of these goals.
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                Author and article information

                Journal
                GRCHFJ
                Green Chemistry
                Green Chem.
                Royal Society of Chemistry (RSC)
                1463-9262
                1463-9270
                2015
                2015
                : 17
                : 7
                : 4068-4072
                Affiliations
                [1 ]Department of Chemistry
                [2 ]Indian Institute of Technology Roorkee
                [3 ]Roorkee-247667
                [4 ]India
                Article
                10.1039/C5GC00403A
                ff399dfd-b113-4993-a92e-4cd273bfdf68
                © 2015
                History

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