103-17-3Relevant articles and documents
Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications
Clarke, Aimee K.,Parkin, Alison,Rossi-Ashton, James A.,Taylor, Richard J. K.,Unsworth, William P.
, p. 5814 - 5820 (2020)
The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.
Synthesis of Air-stable, Odorless Thiophenol Surrogates via Ni-Catalyzed C?S Cross-Coupling
Magné, Valentin,Ball, Liam T.
, p. 8903 - 8910 (2019/06/17)
Thiophenols are versatile synthetic intermediates whose practical appeal is marred by their air sensitivity, toxicity and extreme malodor. Herein we report an efficient catalytic method for the preparation of S-aryl isothiouronium salts, and demonstrate that these air-stable, odorless solids serve as user-friendly sources of thiophenols in synthesis. Diverse isothiouronium salts featuring synthetically useful functionality are readily accessible by nickel-catalyzed C?S cross-coupling of (hetero)aryl iodides and thiourea. Convenient, chromatography-free isolation of these salts is achieved by precipitation, allowing the methodology to be applied directly to large scales. Thiophenols are liberated from the corresponding isothiouronium salts upon treatment with a weak base, enabling an in situ release/S-functionalization strategy that entirely negates the need to isolate, purify or manipulate these noxious reagents.
Synthesis of thioethers via metal-free reductive coupling of tosylhydrazones with thiols
Ding, Qiuping,Cao, Banpeng,Yuan, Jianjun,Liu, Xianjin,Peng, Yiyuan
supporting information; experimental part, p. 748 - 751 (2011/03/22)
A metal-free procedure for the synthesis of thioethers is described via the base-promoted reductive coupling of tosylhydrazones with thiols through an insertion of a carbene into the S-H bond.
