Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex

Arisawa, Mieko; Sawahata, Kyosuke; Ichikawa, Takuya; Yamaguchi, Masahiko

doi:10.1021/acs.organomet.8b00498

Cited by 7 publications

(6 citation statements)

References 28 publications

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“…This approach has limited use in the precise synthesis of complex 1,4-dithiins, as statistical mixtures of starting material and product are formed. 54 Excess 49 can be used to form dithiin 52 ; however, the requisite high temperatures resulted in significant extrusion of sulfur, forming thiophenes as mixtures of isomers. 54 Further development of this methodology is required to produce products in sufficient yield for further diversification.…”

Section: Synthesis Of 14-dithiins and Thianthrenesmentioning

confidence: 99%

“…54 Excess 49 can be used to form dithiin 52 ; however, the requisite high temperatures resulted in significant extrusion of sulfur, forming thiophenes as mixtures of isomers. 54 Further development of this methodology is required to produce products in sufficient yield for further diversification.…”

Section: Synthesis Of 14-dithiins and Thianthrenesmentioning

confidence: 99%

“…Each substituent must be installed in separate reactive sequences, and addition of a third substituent would likely result in mixtures of products, unless the first two substituents added are identical. 54 We believe the application of 1,4-dithiins in materials has been significantly hampered by the limited number of methods available to access various analogues. Further work may aid in enhancing access to these unique heterocycles.…”

Section: Synthesis Of 14-dithiins and Thianthrenesmentioning

confidence: 99%

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The Properties, Synthesis, and Materials Applications of 1,4-Dithiins and Thianthrenes

Swager¹,

Etkind²

2022

Synthesis

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Abstract1,4-Dithiin and its dibenzo-analogue, thianthrene, represent a class of non-aromatic, sulfur-rich heterocycles. Their unique properties, stemming from both their non-planar structures and reversible one- and two-electron oxidations, serve as primary motivators for their use in the development of new materials. The applications of 1,4-dithiins and thianthrenes are rich and diverse, having been used for energy storage and harvesting, and the synthesis of phosphorescent compounds and porous polymers, among other uses. This review offers first an overview of the properties of 1,4-dithiin and thianthrene. Next, we describe enabling synthetic methodology to access 1,4-dithiins and thianthrenes with various substitution patterns. Lastly, the utility of 1,4-dithiin and thianthrene in the construction and design of new materials is detailed using select literature examples.1 Introduction2 Properties of 1,4-Dithiins and Thianthrenes3 Synthesis of 1,4-Dithiins and Thianthrenes3.1 Synthesis of 1,4-Dithiins3.2 Synthesis of Thianthrenes4 Application of 1,4-Dithiins and Thianthrenes in Materials4.1 Thianthrene-Containing Polymers4.2 Thianthrene in Redox-Active Materials4.3 Thianthrenes and 1,4-Dithiins in Supramolecular Chemistry and Self-Assembly4.4 Thianthrenes in Phosphorescent Materials4.5 Thianthrenes with Other Interesting Photophysical Properties4.6 Thianthrenes in the Synthesis of Non-natural Products5 Conclusion

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Section: Synthesis Of 14-dithiins and Thianthrenesmentioning

confidence: 99%

Section: Synthesis Of 14-dithiins and Thianthrenesmentioning

confidence: 99%

Section: Synthesis Of 14-dithiins and Thianthrenesmentioning

confidence: 99%

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The Properties, Synthesis, and Materials Applications of 1,4-Dithiins and Thianthrenes

Swager¹,

Etkind²

2022

Synthesis

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“…2,5-Disubstituted 1,4-dithiines undergo rearrangement to provide 2,6-disubstituted derivatives, which involves the cleavage of two C-S bonds ( Scheme 46 ) [ 91 ]. The reaction requires rhodium catalysis and is under chemical equilibrium.…”

Section: Reversible Nature Of Rhodium-catalyzed C-s Bond Formationmentioning

confidence: 99%

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Arisawa

Yamaguchi

2020

Molecules

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Organosulfur compounds are widely used for the manufacture of drugs and materials, and their synthesis in general conventionally employs nucleophilic substitution reactions of thiolate anions formed from thiols and bases. To synthesize advanced functional organosulfur compounds, development of novel synthetic methods is an important task. We have been studying the synthesis of organosulfur compounds by transition-metal catalysis using disulfides and sulfur, which are easier to handle and less odiferous than thiols. In this article, we describe our development that rhodium complexes efficiently catalyze the cleavage of S-S bonds and transfer organothio groups to organic compounds, which provide diverse organosulfur compounds. The synthesis does not require use of bases or organometallic reagents; furthermore, it is reversible, involving chemical equilibria and interconversion reactions.

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“…45 During the study of the synthesis of 1,4-dithiins using rhodium catalyst, we developed isomerization and alkyne exchange reactions of 1,4-dithiines involving the cleavage of two sp 2 C-S bonds (Scheme 26). 46 The 1,5-disubstituted 1,4-dithiins isomerize to 2,6-disubstituted 1,4-dithiins in toluene at 110 °C via sp 2 C-S bond cleavage in the presence of a rhodium catalyst to give equilibrium mixtures of isomers. The 2,6-disubstituted dithiins are also isomerized to 1,5-disubstituted 1,4-dithiins under rhodium catalysis.…”

Section: Scheme 24 Reaction Of Dithiorhodium Complex and Cyclooctyne 18mentioning

confidence: 99%

Rhodium-Catalyzed Synthesis of Organosulfur Compounds using Sulfur

Arisawa

Yamaguchi

2019

Synlett

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Sulfur is one of the few elements that occurs uncombined in nature. Sulfur atoms are found in natural amino acids and vitamins. In the chemical industry, organosulfur compounds are used for fabricating rubber, fibers, and dyes, pharmaceuticals, and pesticides. Although sulfur, which is cheap and easy to handle, is a useful source of sulfur atom in functional organosulfur compounds, it is rarely used in organic synthesis. Activation of sulfur by high temperature, light irradiation, treatment with nucleophiles and electrophiles, and redox conditions often results in the formation of various active sulfur species, which complicate reactions. The development of a method that mildly activates sulfur is therefore desired. The use of transition-metal catalysts is a new method of activating sulfur under mild conditions, and, in this article, we describe the rhodium-catalyzed synthesis of various organosulfur compounds by the insertion of sulfur atoms into single bonds and by the addition of sulfur to unsaturated bond in various organic compounds.1 Introduction2 Sulfur Activation without using Transition Metal3 Transition-Metal-Catalyzed Activation of Sulfur4 Rhodium-Catalyzed Reactions using Sulfur4.1 Rhodium-Catalyzed Sulfur Atom Exchange Reactions using Sulfur4.2 Synthesis of Diaryl Sulfides using Rhodium-Catalyzed Exchange Reaction of Aryl Fluorides and Sulfur/Organopolysulfides4.3 Rhodium-Catalyzed Synthesis of Isothiocyanate using Sulfur4.4 Rhodium-Catalyzed Sulfur Addition Reaction to Alkenes for Thiiranes Synthesis4.5 Rhodium-Catalyzed Sulfur Addition Reaction to Alkynes for 1,4-Dithiins Synthesis5 Conclusion

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Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex

Cited by 7 publications

References 28 publications

The Properties, Synthesis, and Materials Applications of 1,4-Dithiins and Thianthrenes

The Properties, Synthesis, and Materials Applications of 1,4-Dithiins and Thianthrenes

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Rhodium-Catalyzed Synthesis of Organosulfur Compounds using Sulfur

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