Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates

Miura, Hideo; Toyomasu, Tomoya; Nishio, Hidenori; Shishido, Tetsuya

doi:10.1039/d1cy02085d

Cited by 2 publications

(2 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2022, the thioetherification of allyl, benzyl, and propargyl phosphates was published ( Scheme 55 ) [ 208 ]. The reaction’s scope was exclusively evaluated using silylated thiophenol.…”

Section: Transition-metal-catalyzed Allylic and Benzylic Substitution...mentioning

confidence: 99%

Organophosphates as Versatile Substrates in Organic Synthesis

Oeser,

Tobrman

2024

Molecules

View full text Add to dashboard Cite

This review summarizes the applications of organophosphates in organic synthesis. After a brief introduction, it discusses cross-coupling reactions, including both transition-metal-catalyzed and transition-metal-free substitution reactions. Subsequently, oxidation and reduction reactions are described. In addition, this review highlights the applications of organophosphates in the synthesis of natural compounds, demonstrating their versatility and importance in modern synthetic chemistry.

show abstract

Section: Transition-metal-catalyzed Allylic and Benzylic Substitution...mentioning

confidence: 99%

Organophosphates as Versatile Substrates in Organic Synthesis

Oeser,

Tobrman

2024

Molecules

View full text Add to dashboard Cite

show abstract

“…On the other hand, heterogeneous catalysts, especially supported metal catalysts, are widely used for manufacturing not only bulk chemicals but also fine chemicals in the chemical industry, thanks to their high stability and insolubility in organic and inorganic media . For instance, supported gold nanoparticle catalysts have been reported to show excellent catalysis toward carbon–heteroatom bond formations . Furthermore, recent studies on the cooperation between the redox properties of metal nanoparticles and the acid–base function of the support explored novel perspectives on supported catalysts toward selective molecular transformations .…”

Section: Introductionmentioning

confidence: 99%

Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp³)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

et al. 2023

Self Cite

View full text Add to dashboard Cite

Since C(sp3)–O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of C(sp3)–O bonds will be a key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides, namely, ZrO2, efficiently generated alkyl radicals via homolysis of unactivated C(sp3)–O bonds, which consequently promoted C(sp3)–Si bond formation to give diverse organosilicon compounds. A wide array of esters and ethers, which are either commercially available or easily synthesized from alcohols participated in the heterogeneous gold-catalyzed silylation by disilanes to give diverse alkyl-, allyl-, benzyl-, and allenyl silanes in high yields. In addition, this novel reaction technology for C(sp3)–O bond transformation could be applied to the upcycling of polyesters, i.e., the degradation of polyesters and the synthesis of organosilanes were realized concurrently by the unique catalysis of supported gold nanoparticles. Mechanistic studies corroborated the notion that the generation of alkyl radicals is involved in C(sp3)–Si coupling and the cooperation of gold and an acid–base pair on ZrO2 is responsible for the homolysis of stable C(sp3)–O bonds. The high reusability and air tolerance of the heterogeneous gold catalysts as well as a simple, scalable, and green reaction system enabled the practical synthesis of diverse organosilicon compounds.

show abstract

Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates

Abstract: Gold-catalyzed thioetherification of C(sp3)–O bonds is described. The reaction of allyl phosphates and thiosilanes in the presence of gold nanoparticles supported on ZrO2 proceeded efficiently under mild reaction conditions to...

Cited by 2 publications

References 52 publications

Organophosphates as Versatile Substrates in Organic Synthesis

Organophosphates as Versatile Substrates in Organic Synthesis

Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp³)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

Contact Info

Product

Resources

About

Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates

Abstract: Gold-catalyzed thioetherification of C(sp3)–O bonds is described. The reaction of allyl phosphates and thiosilanes in the presence of gold nanoparticles supported on ZrO2 proceeded efficiently under mild reaction conditions to...

Cited by 2 publications

References 52 publications

Organophosphates as Versatile Substrates in Organic Synthesis

Organophosphates as Versatile Substrates in Organic Synthesis

Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp3)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

Contact Info

Product

Resources

About

Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp³)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides