54835-27-7Relevant academic research and scientific papers
Copper-catalyzed cyanothiolation to incorporate a sulfur-substituted quaternary carbon center
Huang, Yubing,Li, Xianwei,Wang, Xu,Yu, Yue,Zheng, Jia,Wu, Wanqing,Jiang, Huanfeng
, p. 7047 - 7051 (2017)
Sulfur-containing nitriles have important research value in the life sciences due to their diverse biological activities resulting from the sulfur and cyano functional groups. Herein, a copper-catalyzed cyanothiolation of N-tosylhydrazones with thiocyanates to generate α-arylthioalkanenitriles bearing sulfur-substituted quaternary carbon center atoms has been described. This novel protocol involves the procedure of copper carbene species promoting S-CN bond cleavage and C-CN/C-S bond reconstruction to introduce both sulfur and cyano groups onto a single carbon center. This cyanothiolation reaction will greatly enhance the synthetic utility of carbenoid species as new entries for the construction of diverse heteroatom-containing nitriles via cyanofunctionalization of metal-carbene species.
THE REDUCTIVE LITHIATION OF THIOACETALS, α,α-BIS(TRIMETHYLSILYL)-ALKYL SULFIDES, AND 2-ALKYL-2-ETHYLTHIOALKANENITRILES USING TRIBUTYLSTANNYLLITHIUM
Takeda, Takeshi,Ando, Kazuo,Mamada, Akira,Fujiwara, Tooru
, p. 1149 - 1152 (2007/10/02)
The reaction of thioacetals of phenyl ketones, α,α-bis(trimethylsilyl)alkyl sulfides, and 2-alkyl-2-ethylthioalkanenitriles with tributhylstannyllithium gave the corresponding α-anions of sulfides, α,α-bis(trimethylsilyl)alkane, and nitriles, respectively.
Oxidative Decyanation of Secondary Nitriles to Ketones
Freerksen, Robert W.,Selikson, Sandra J.,Wroble, Randall R.,Kyler, S. Keith,Watt, David S.
, p. 4087 - 4096 (2007/10/02)
Procedures for the oxidative decyanation of secondary nitriles to ketones involve (1) iodination of N-(trialkylsilyl)ketenimines derived from secondary nitriles and subsequent hydrolysis of the α-iodo nitriles with silver oxide, (2) addition of nitrosobenzene to N-(trialkylsilyl)ketenimines, (3) conversion of secondary nitriles to α-(phenylthio) nitriles and subsequent hydrolysis with N-bromosuccinimide in aqueous acetonitrile, and (4) preparation of α-hydroperoxy nitriles by direct oxygenation of anions of secondary nitriles and subsequent reductive hydrolysis with stannous chloride followed by sodium hydroxide.The latter general procedure was applied to various secondary nitriles bearing dialkyl, aryl and alkyl, and diaryl substituents to provide ketones in good yield and was extended to the oxidative decyanation of α,β-unsaturated nitriles to furnish α,β-unsaturated ketones.
