658-00-4Relevant articles and documents
Integrating hydrogen production with anodic selective oxidation of sulfides over a CoFe layered double hydroxide electrode
Ma, Lina,Zhou, Hua,Xu, Ming,Hao, Peipei,Kong, Xianggui,Duan, Haohong
, p. 938 - 945 (2021)
Replacing the sluggish oxygen evolution reaction (OER) with oxidation reactions for the synthesis of complex pharmaceutical molecules coupled with enhanced hydrogen evolution reaction (HER) is highly attractive, but it is rarely explored. Here, we report an electrochemical protocol for selective oxidation of sulfides to sulfoxides over a CoFe layered double hydroxide (CoFe-LDH) anode in an aqueous-MeCN electrolyte, coupled with 2-fold promoted cathodic H2productivity. This protocol displays high activity (85-96% yields), catalyst stability (10 cycles), and generality (12 examples) in selective sulfide oxidation. We demonstrate its applicability in the synthesis of four important pharmaceutical related sulfoxide compounds with scalability (up to 1.79 g). X-ray spectroscopy investigations reveal that the CoFe-LDH material evolved into amorphous CoFe-oxyhydroxide under catalytic conditions. This work may pave the way towards sustainable organic synthesis of valuable pharmaceuticals coupled with H2production.
Metal- and additive-free oxygen-atom transfer reaction: an efficient and chemoselective oxidation of sulfides to sulfoxides with cyclic diacyl peroxides
Gan, Shaoyan,Yin, Junjie,Yao, Yuan,Liu, Yang,Chang, Denghu,Zhu, Dan,Shi, Lei
supporting information, p. 2647 - 2654 (2017/04/03)
Metal- and additive-free oxidation of a series of sulfides/thioketones has been achieved using cyclic diacyl peroxides as mild oxygen sources. This protocol features simple manipulation, high chemo- and diastereoselectivity, and a broad substrate scope (up to 42 examples), tolerates many common functional groups, and is scalable and applicable to the late-stage sulfoxidation strategy. A preliminary mechanistic study by quantum mechanical calculations suggests that a single two-electron transfer process is energetically more favorable, and indicates the reactivity of cyclic diacyl peroxides distinct from conventional acyclic acyl peroxides.
Proximal effect of the nitrogen bases in the oxidative decarboxylation of phenylsulfinylacetic acids by oxo(salen)chromium(V) complexes
Subramaniam,Sugirtha Devi,Anbarasan
, p. 159 - 168 (2014/06/24)
Oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) and several substituted PSAAs with three oxo(salen)chromium(V) complexes in the presence of nitrogen bases are investigated in 100% acetonitrile medium using spectrophotometric technique. The nitrogenous bases such as imidazole, 1-methyl imidazole and pyridine catalyse the reaction and Michaelis-Menten kinetics is observed with respect to these bases. Among the various bases employed, imidazole with strong π donating ability shows the least accelerating effect and the maximum catalytic activity is observed with pyridine. Both the electron donating and electron withdrawing substituents in PSAA accelerate the reaction rate. The Hammett plots for the three oxo(salen)chromium(V) complexes with three nitrogen bases display a nonlinear upward curvature. The Hammett parameter ρ, changes from large negative to small positive values as the substituents are changed from electron donating to electron withdrawing groups. A mechanism involving direct oxygen transfer from oxo(salen)chromium(V)-nitrogen base adduct to PSAA with simultaneous decarboxylation to yield sulfone is proposed. The nonlinear Hammett plot has been ascribed to a shift in the rate determining step caused by the formation and decomposition of the sulfonium ion intermediate which is susceptible to substituent effect.
