- Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes
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Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.
- Liu, Richard Y.,Bae, Minwoo,Buchwald, Stephen L.
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supporting information
p. 1627 - 1631
(2018/02/17)
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- Electron transfer in the peroxytrifluoroacetic acid-assisted sulfoxidation and oxidative destruction of benzhydryl sulfides
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The reactions of benzhydryl sulfides Ph2CHSCH2R (R = H, CONH2, COOH, CN) with peroxytrifluoroacetic acid in CF 3COOH were studied experimentally and by the quantum chemical density functional theory (DFT) method and exhibited an unusual dependence on the substituent R. When R≠H, a complicated oxidative destruction of the substrates occurs to form 2,4,6-tribenzhydrylphenol as one of the products, while in the case of R = H, the starting benzhydryl sulfide is smoothly sulfoxidated. This fact is due to the common electron transfer from the substrate to reagent at the initial step and the difference in subsequent transformations of the species formed.
- Akopova,Morkovnik,Khrustalev,Bicherov
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p. 1164 - 1175
(2014/03/21)
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- Simple synthesis of modafinil derivatives and their anti-inflammatory activity
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Simple synthesis of modafinil derivatives and their biological activity are described. The key synthetic strategies involve substitution and coupling reactions. We determined the anti-inflammatory effects of modafinil derivatives in cultured BV2 cells by measuring the inhibition of nitrite production and expression of iNOS and COX-2 after LPS stimulation. It was found that for sulfide analogues introduction of aliphatic groups on the amide part (compounds 11a-d) resulted in lower anti-inflammatory activity compared with cyclic or aromatic moieties (compounds 11e-k). However, for the sulfoxide analogues, introduction of aliphatic moieties (compounds 12a-d) showed higher anti-inflammatory activity than cyclic or aromatic fragments (compounds 12e-k) in BV-2 microglia cells.
- Jung, Jae-Chul,Lee, Yeonju,Son, Jee-Young,Lim, Eunyoung,Jung, Mankil,Oh, Seikwan
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p. 10446 - 10458
(2012/11/07)
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