62291-59-2Relevant academic research and scientific papers
Electrochemical and direct C-H methylthiolation of electron-rich aromatics
Wu, Yaxing,Ding, Hongliang,Zhao, Ming,Ni, Zhong-Hai,Cao, Jing-Pei
supporting information, p. 4906 - 4911 (2020/08/25)
The electrochemical-induced C-H methylthiolation of electron-rich aromatics has been accomplished via a three component cross-coupling strategy. Potassium thiocyanate (KSCN) as both the supporting electrolyte and sulfur source and methanol as the methylation reagent are used. This protocol is versatile for various (hetero)aromatic compounds such as aniline, anisole and indole. The reaction proceeds under mild conditions without any metal catalyst, exogenous oxidant and highly toxic sulfur reagent. Importantly, such an electrochemical-induced methylthiolated reaction could be easily scaled up with good efficiency.
C-H Alkenylation of Heteroarenes: Mechanism, Rate, and Selectivity Changes Enabled by Thioether Ligands
Gorsline, Bradley J.,Wang, Long,Ren, Peng,Carrow, Brad P.
supporting information, p. 9605 - 9614 (2017/07/24)
Thioether ancillary ligands have been identified that can greatly accelerate the C-H alkenylation of O-, S-, and N-heteroarenes. Kinetic data suggest thioether-Pd-catalyzed reactions can be as much as 800× faster than classic ligandless systems. Furthermore, mechanistic studies revealed C-H bond cleavage as the turnover-limiting step, and that rate acceleration upon thioether coordination is correlated to a change from a neutral to a cationic pathway for this key step. The formation of a cationic, low-coordinate catalytic intermediate in these reactions may also account for unusual catalyst-controlled site selectivity wherein C-H alkenylation of five-atom heteroarenes can occur under electronic control with thioether ligands even when this necessarily involves reaction at a more hindered C-H bond. The thioether effect also enables short reaction times under mild conditions for many O-, S-, and N-heteroarenes (55 examples), including examples of late-stage drug derivatization.
Metallation reactions XXVII. Metallation of (methylthio)anilines
Cabiddu,Cabiddu,Cadoni,Cannas,De Montis,Fattuoni,Melis
, p. 263 - 275 (2007/10/03)
The metallation reactions of (methylthio)anilines with organolithium reagents and with the butyllithium-potassium tert-butoxide superbasic mixture are here described. The results show that the para isomer when treated with butyllithium gave a mixture of p
