- Catalyst-free generation of acyl radicals induced by visible light in water to construct C-N bonds
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We describe herein a catalyst-free and redox-neutral photochemical strategy for the direct generation of acyl radicals from α-diketones, and its selective conversion of nitrosoarenes to hydroxyamides or amides with AcOH or NaCl as an additive. The reaction was carried out under mild conditions in water with purple LEDs as the light source. A broad scope of substrates was demonstrated. Mechanistic experiments indicate that α-diketones cleave to give acyl radicals, with hydroxyamides being further reduced to amides.
- Ran, Maogang,He, Jiaxin,Yan, Boyu,Liu, Wenbo,Li, Yi,Fu, Yunfen,Li, Chao-Jun,Yao, Qiuli
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supporting information
p. 1970 - 1975
(2021/03/16)
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- Synthesis method of N-acylhydroxylamine
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The invention relates to a synthesis method of N-acylhydroxylamine, which comprises the following steps: starting from o-diketone and a nitroso compound, and adding an acid thereby efficiently obtaining the structure of N-acylhydroxylamine under the irradiation of visible light or ultraviolet light, wherein a part of the obtained product is an important biomedical chemical intermediate. Accordingto the method, the o-diketone and the nitroso compound which are cheap and easy to obtain are used as raw materials, only visible light or ultraviolet light irradiation is needed, cheap acid is addedin the reaction process, a catalyst or a metal compound is not needed, and only water can be used as a solvent in mass production. The whole production process is environmentally friendly, economical,efficient and low in cost, and has very remarkable advantages compared with the conventional production process.
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Paragraph 0059-0061
(2020/09/30)
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- Hydroxamic Acids as Chemoselective (ortho-Amino)arylation Reagents via Sigmatropic Rearrangement
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The use of readily available hydroxamic acids as reagents for the chemoselective (ortho-amino)arylation of amides is described. This reaction proceeds under metal-free, mild conditions, displays a very broad scope, and constitutes a direct approach for the metal-free attachment of aniline residues to carbonyl derivatives.
- Shaaban, Saad,Tona, Veronica,Peng, Bo,Maulide, Nuno
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supporting information
p. 10938 - 10941
(2017/08/30)
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- DXP synthase-catalyzed c-n bond formation: Nitroso substrate specificity studies guide selective inhibitor design
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1-Deoxy-D-xylulose 5-phosphate (DXP) synthase catalyzes the first step in the nonmammalian isoprenoid biosynthetic pathway to form DXP from pyruvate and D-glyceraldehyde 3-phosphate (D-GAP) in a thiamin diphosphate-dependent manner. Its unique structure and mechanism distinguish DXP synthase from its homologues and suggest that it should be pursued as an anti-infective drug target. However, few reports describe any development of selective inhibitors of this enzyme. Here, we reveal that DXP synthase catalyzes C-N bond formation and exploit aromatic nitroso substrates as active site probes. Substrate specificity studies reveal a high affinity of DXP synthase for aromatic nitroso substrates compared to the related ThDP-dependent enzyme pyruvate dehydrogenase (PDH). Results from inhibition and mutagenesis studies indicate that nitroso substrates bind to E. coli DXP synthase in a manner distinct from that of D-GAP. Our results suggest that the incorporation of aryl acceptor substrate mimics into unnatural bisubstrate analogues will impart selectivity to DXP synthase inhibitors. As a proof of concept, we show selective inhibition of DXP synthase by benzylacetylphosphonate (BnAP).
- Morris, Francine,Vierling, Ryan,Boucher, Lauren,Bosch, Juergen,Freel Meyers, Caren L.
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p. 1309 - 1315
(2013/08/23)
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- A Direct Aromatic Methylsulfanylation of N-Aryl-N-methoxyacetamides with an Aluminium Chloride-Dimethyl Sulfide System
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Treatment of N-aryl-N-methoxyacetamides, which bear a strong electron-donating group on the aryl ring, with an AlCl3-Me2S system results in heterocyclic cleavage of the nitrogen-oxygen bond and introduction of a methylsulfanyl group at the ortho or para position of the aryl ring.
- Matsumoto, Kazuhiro,Kato, Miyako,Sakamoto, Takeshi,Kikugawa, Yasuo
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- Novel Reactions: Part I - Facile Synthesis of Substituted ortho-Chloranilines from Nitrobenzene Derivatives
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N-Substituted benzo and acetohydroxamic acids (5), prepared from N-arylhydroxylamines and benzoyl or acetyl chloride, react readily with thionyl chloride at low temperature to give ortho-chloroanilide derivatives (6) in good yield.The latter (6) on hydrolysis give ortho-chloroanilines (10).Since the N-arylhydroxylamines are obtained from nitroarenes by partial reduction, the overall reaction amounts to the preparation of 10 from nitroarenes.
- Ayyangar, N. R.,Kalkote, U. R.,Nikrad, P. V.
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p. 872 - 877
(2007/10/02)
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