23496-29-9Relevant articles and documents
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McKie
, (1924)
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Synthesis and Mechanistic Insights of the Formation of 3-Hydroxyquinolin-2-ones including Viridicatin from 2-Chloro- N,3-diaryloxirane-2-carboxamides under Acid-Catalyzed Rearrangements
Mamedov, Vakhid A.,Mamedova, Vera L.,Qu, Zheng-Wang,Zhu, Hui,Galimullina, Venera R.,Korshin, Dmitry E.,Khikmatova, Gul'Naz Z.,Litvinov, Igor A.,Latypov, Shamil K.,Sinyashin, Oleg G.,Grimme, Stefan
, p. 13514 - 13534 (2021/09/28)
N-Benzyl-2-chloro-N,3-diaryloxirane-2-carboxamides, easily obtained from aromatic aldehydes and anilides of dichloroacetic acid under Darzens condensation conditions, proved to be excellent starting compounds for the synthesis of 3-hydroxyindolin-2-ones, cyclohepto[b]pyrrole-2,3-diones, and 1-azaspiro[4.5]deca-3,6,9-triene-2-ones via the C(sp2)-C(sp2) bond formation in the first case and C(sp2)-C(sp3) bond formation in the second and third cases. Under optimized reaction conditions, 3-hydroxyindolin-2-ones are obtained in a one-pot process, which involves the treatment of N-benzyl-2-chloro-N,3-diaryloxirane-2-carboxamides with CF3CO2H or AcOH/H2SO4. In the case of intramolecular cyclization, the detailed reaction channels depend strongly on the substituents present in the anilide component and in the aromatic ring of the aldehyde component of N-benzyl-2-chloro-N,3-diaryloxirane-2-carboxamides, as well as the temperature and duration of the reaction. A combined experimental and DFT mechanistic study of the formation of 1-benzyl-3-hydroxy-4-arylquinolin-2(1H)-ones showed that there are three competing reaction channels: (a) ring-closure via the ipso site, (b) ring-closure via the 1,2-Cl shift, and (c) ring-closure via the ortho site. Such mechanistic insights enabled an effective one-pot gram-scale synthesis of viridicatin from benzaldehyde and 2,2-dichloro-N-(4-methoxybenzyl)-N-phenylacetamide.
Investigation of the Potential of Molybdenum(VI) Hydrazido(2-) Complexes as Sources of Nitrenium Ions: Cleavage of the N-N Bond and Incorporation of the β-Nitrogen Group into Solvent Molecules
Baum, Marc M.,Smith, Edward H.
, p. 2513 - 2520 (2007/10/02)
Photolyis or thermolysis of bis(N,N-dimethyldithiocarbamato)bismolybdenum(VI) complexes in 1,1,2,2-tetrachloroethane results predominantly in transfer of the hydrazido group to the solvent with formation of dichloroacetohydrazides.A small amount of the corresponding dichloroacetamides are produced by N-N cleavage and N(R)Ph transfer.In contrast, the latter process dominates the reaction of dichlorobis(N,N-dimethyldithiocarbamato)mono-molybdenum(VI) complexes with silver nitrate in alcohols occuring concomitantly with ring methoxylation and nitration and N-nitrosation.Neither transfer of N(R)Ph appears to involve free nitrenium ions.