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Relevant academic research and scientific papers

Alkoxyallene-Based LANCA Three-Component Synthesis of 1,2-Diketones, Quinoxalines, and Unique Isoindenone Dimers and a Computational Study of the Isoindenone Dimerization

A series of β-alkoxy-β-ketoenamides was prepared by the well-established LANCA three-component reaction of lithiated 1-(2-trimethylsilylethoxy)-substituted allenes, nitriles, and α,β-unsaturated carboxylic acids. The α-tert-butyl-substituted compounds were smoothly converted into the expected 1,2-diketones by treatment with trifluoroacetic acid. A subsequent condensation of the 1,2-diketones with o-phenylenediamine provided the desired highly substituted quinoxalines in good overall yield. Surprisingly, the α-phenyl-substituted β-alkoxy-β-ketoenamides investigated afford not only the expected 1,2-diketones, but also pentacyclic compounds with an anti-tricyclo[4.2.1.12,5]deca-3,7-diene-9,10-dione core. These interesting products are very likely the result of an isoindenone dimerization which was mechanistically studied with the support of DFT calculations. Under the strongly acidic reaction conditions, a stepwise reaction is likely leading to a protonated isoindenone as reactive intermediate. It may first form a van der Waals complex with a neutral isoindenone before the two regio- and diastereoselective ring forming steps occur. Interestingly, two neutral or two protonated isoindenones are also predicted to dimerize giving the observed pentacyclic product.||||||.

Metal-free syntheses of oxazoles and their analogues based on λ3-iodane-mediated cycloisomerization/functionalization reactions or [2+2+1] cycloaddition type reactions

As a metal-free construction of oxazoles and furans concomitant with the introduction of oxygen functional groups or fluorine atoms into the side chains, we have developed λ3-iodane-mediated cycloisomerization/functionalization reactions of propargyl compounds. In these reactions, aryl- λ3-iodane ArI(X)Y works not only as a donor of heteroatomic functional groups but also as an activator of carbon-carbon triple bonds. Therefore, this methodology is not required any transition metal catalysts, which are frequently used in previous methods. Furthermore, this methodology can be extended to λ3-iodane-mediated [2+2+1] cycloaddition type reactions of alkynes, nitriles and heteroatoms for metal-free formation of oxazoles and imidazoles.

Iodine(III)-Catalyzed Formal [2 + 2 + 1] Cycloaddition Reaction for Metal-Free Construction of Oxazoles

The iodine(III) catalyst, in situ generated from iodoarene as a precatalyst with m-CPBA and Tf2NH, promoted the metal-free [2 + 2 + 1] cycloaddition-type reactions of alkynes, nitriles, and oxygen atoms for the regioselective formations of 2,4-disubstituted and 2,4,5-trisubstituted oxazole. A first example of iodine catalysis for multicomponent reactions is represented.

Metal-free [2 + 2 + 1] annulation of alkynes, nitriles, and oxygen atoms: Iodine(III)-mediated synthesis of highly substituted oxazoles

The metal-free [2 + 2 + 1] annulation of alkynes, nitriles, and O-atoms for the regioselective assembly of 2,4-disubstituted and 2,4,5-trisubstituted oxazole compounds has been achieved by the use of PhIO with TfOH or Tf 2NH. The present reaction could be applied to a facile synthesis of an anti-inflammatory drug.