171897-90-8Relevant academic research and scientific papers
Rhodium-catalyzed α-methylthiolation reaction of unactivated ketones using 1,2-diphenyl-2-methylthio-1-ethanone for the methylthio transfer reagent
Arisawa, Mieko,Toriyama, Fumihiko,Yamaguchi, Masahiko
experimental part, p. 2305 - 2312 (2011/04/22)
In the presence of catalytic amounts of RhH(PPh3)4, 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, ketones without α-activating groups were α-methylthiolated with 1,2-diphenyl-2-methylthio-1-ethanone giving α-methylthio ketones. The reaction of unsymmetrical ketones proceeded at the more substituted carbons. The initial formation of kinetic α-methylthiolated products followed by their rearrangement to thermodynamic products was observed in the reaction of α-phenyl ketones. Aldehydes, phenylacetate, and phenylacetonitrile were also α-methylthiolated under these conditions.
Synthesis of Trimethyl α-Keto Trithioorthoesters and Dimethyl α-Keto Dithioacetals by Reaction of Esters with Tris(methylthio)methyllithium
Barbero, Margherita,Cadamuro, Silvano,Degani, Iacopo,Dughera, Stefano,Fochi, Rita
, p. 6017 - 6024 (2007/10/03)
A complete study has been made of the reaction of tris(methylthio)methyllithium with aromatic, heteroaromatic, and aliphatic esters.It is a one-pot reaction that despite its complexity, and depending on the reagent ratios, the reaction conditions, and the possible use of additional reagents (N-(methylthio)phthalimide or BuLi), can supply easily, in excellent and reproducible yields, the trimethyl α-keto trithioorthoesters 3 or, alternatively, the dimethyl α-keto dithioacetals 4.The reaction mechanism has been elucidated.
