scholarly journals Synthesis of Aryl Sulfides by Metal-Free Arylation of Thiols with Diaryliodonium Salts

2021 ◽  
Author(s):  
Sudeep Sarkar ◽  
Natalia Wojciechowska ◽  
Adam A. Rajkiewicz ◽  
Marcin Kalek
Keyword(s):  
Dft Calculations ◽  
Bond Formation ◽  
Reductive Elimination ◽  
Organic Base ◽  
Metal Free ◽  
Diaryliodonium Salts ◽  
Inner Sphere ◽  
Aryl Sulfides ◽  
Mechanism Of The Reaction

Metal-free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base ena-bles the C–S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that is follows the inner sphere pathway involv-ing the incipient formation of Ar2I(SR) intermediate, followed by the reductive elimination.

scholarly journals A mild carbon–boron bond formation from diaryliodonium salts

2015 ◽  
Vol 51 (74) ◽  
pp. 14068-14071 ◽  
Author(s):  
N. Miralles ◽  
R. M. Romero ◽  
E. Fernández ◽  
K. Muñiz
Keyword(s):  
Bond Formation ◽  
Metal Free ◽  
Diaryliodonium Salts ◽  
Boronic Esters

Metal-free borylation of diaryliodonium salts with diboron reagents toward formation of aryl boronic esters and concomitant two-step C–C coupling of both aryl groups of the initial diaryliodonium reagent.

Rapid synthesis of aryl sulfides through metal-free C–S coupling of thioalcohols with diaryliodonium salts

2014 ◽  
Vol 55 (42) ◽  
pp. 5739-5741 ◽  
Author(s):  
Dawei Wang ◽  
Xin Yu ◽  
Keyan Zhao ◽  
Liang Li ◽  
Yuqiang Ding
Keyword(s):  
Rapid Synthesis ◽  
Metal Free ◽  
Diaryliodonium Salts ◽  
Aryl Sulfides

Safe and Metal-Free Synthesis of 1-Alkenyl Aryl Sulfides and Their Sulfones from Thiiranes and Diaryliodonium Salts

Synthesis ◽  
2018 ◽  
Vol 50 (12) ◽  
pp. 2407-2415 ◽  
Author(s):  
Jiaxi Xu ◽  
Jun Dong
Keyword(s):  
Reaction Mechanism ◽  
Ring Opening ◽  
Hydrogen Abstraction ◽  
Current Method ◽  
Performic Acid ◽  
Nucleophilic Attack ◽  
Safe Method ◽  
Metal Free ◽  
Diaryliodonium Salts ◽  
Aryl Sulfides

A series of 1-alkenyl aryl sulfides was synthesized from thiiranes and diaryliodonium salts in tetrahydrofuran in the presence of potassium tert-butoxide. The proposed reaction mechanism involves generation of benzynes from the diaryliodonium salts in the presence of the base. Then, nucleophilic attack of the benzynes by thiiranes, followed by hydrogen abstraction and ring opening of the generated thiiranium intermediates, provides the sulfides. These sulfides were further oxidized with performic acid to the corresponding sulfones. The current method provides a metal-free and safe method for the preparation of 1-alkenyl aryl sulfides and their sulfones.

ChemInform Abstract: Rapid Synthesis of Aryl Sulfides Through Metal-Free C-S Coupling of Thioalcohols with Diaryliodonium Salts.

ChemInform ◽  
2015 ◽  
Vol 46 (15) ◽  
pp. no-no
Author(s):  
Dawei Wang ◽  
Xin Yu ◽  
Keyan Zhao ◽  
Liang Li ◽  
Yuqiang Ding
Keyword(s):  
Rapid Synthesis ◽  
Metal Free ◽  
Diaryliodonium Salts ◽  
Aryl Sulfides

Stereodivergent Alkyne Hydrofluorination Using a Simple Practical Reagent

2020 ◽  
Author(s):  
Rui Guo ◽  
Xiaotian Qi ◽  
Hengye Xiang ◽  
Paul Geaneoates ◽  
Ruihan Wang ◽  
...  
Keyword(s):  
Bond Formation ◽  
Biologically Active ◽  
Dft Studies ◽  
Thermodynamic Control ◽  
Important Goal ◽  
Peptide Bonds ◽  
Metal Free ◽  
Vinyl Cation ◽  
E And Z Isomers ◽  
Vinyl Fluorides

Vinyl fluorides play an important role in drug development as they serve as bioisosteres for peptide bonds and are found in a range of biologically active molecules. The discovery of safe, general and practical procedures to prepare vinyl fluorides remains an important goal and challenge for synthetic chemistry. Here we introduce an inexpensive and easily-handled reagent and report simple, scalable, and metal-free protocols for the regioselective and stereodivergent hydrofluorination of alkynes to access both the E and Z isomers of vinyl fluorides. These conditions were suitable for a diverse collection of alkynes, including several highly-functionalized pharmaceutical derivatives. Mechanistic and DFT studies support C–F bond formation through a vinyl cation intermediate, with the (E)- and (Z)-hydrofluorination products forming under kinetic and thermodynamic control, respectively.<br>

Reversible Oxidative-Addition and Reductive-Elimination of Thiophene from a Titanium Complex and Its Thermally-Induced Hydrodesulfurization Chemistry

2019 ◽  
Author(s):  
Alejandra Gomez-Torres ◽  
J. Rolando Aguilar-Calderón ◽  
Carlos Saucedo ◽  
Aldo Jordan ◽  
Alejandro J. Metta-Magaña ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Ring Opening ◽  
Thiophene Ring ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Thermally Induced ◽  
Titanium Complex

<p>The masked Ti(II) synthon (<sup>Ket</sup>guan)(<i>η</i><sup>6</sup>-Im<sup>Dipp</sup>N)Ti (<b>1</b>) oxidatively adds across thiophene to give ring-opened (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti[<i>κ</i><sup>2</sup>-<i>S</i>(CH)<sub>3</sub><i>C</i>H] (<b>2</b>). Complex <b>2</b> is photosensitive, and upon exposure to light, reductively eliminates thiophene to regenerate <b>1</b> – a rare example of early-metal mediated oxidative-addition/reductive-elimination chemistry. DFT calculations indicate strong titanium π-backdonation to the thiophene π*-orbitals leads to the observed thiophene ring opening across titanium, while a proposed photoinduced LMCT promotes the reverse thiophene elimination from <b>2</b>. Finally, pressurizing solutions of <b>2 </b>with H<sub>2</sub> (150 psi) at 80 °C leads to the hydrodesulfurization of thiophene to give the Ti(IV) sulfide (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti(S) (<b>3</b>) and butane. </p>

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