- Palladium-Catalyzed Aminocyclization-Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study
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Dehydrotryptophan derivatives have been prepared by palladium-catalyzed aminocyclization-Heck-type coupling cascades starting from o-alkynylaniline derivatives and methyl α-aminoacrylate. Aryl, alkyl (primary, secondary, and tertiary), and alkenyl substituents have been introduced at the indole C-2 position. Further variations at the indole benzene ring, as well as the C-2-unsubstituted case, have all been demonstrated. In the case of C-2 aryl substitution, the preparation of the o-alkynylaniline substrate by Sonogashira coupling and the subsequent cyclization-coupling cascade have been performed in a one-pot protocol with a single catalyst. DFT calculations have revealed significant differences in the reaction profiles of these reactions relative to those involving methyl acrylate or methacrylate, and between the reactions of the free anilines and their corresponding carbamates. Those calculations suggest that the nature of the alkene and of the acid HX released in the HX/alkene exchange step that precedes C-C bond formation could be responsible for the experimentally observed differences in reaction efficiencies.
- Vaz, Belén,Martínez, Claudio,Cruz, Francisco,Denis, J. Gabriel,De Lera, ángel R.,Aurrecoechea, José M.,álvarez, Rosana
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p. 8766 - 8785
(2021/06/30)
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- Synthesis of 7-alkylidene-7,12-dihydroindolo[3,2-d]benzazepine-6-(5H)-ones (7-alkylidene-paullones) by N-cyclization-oxidative Heck cascade and characterization as sirtuin modulators
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An extension of our reported protocol to benzofused heterocyclic derivatives (benzofurans, indoles, isochromeneimines), involving a palladium-induced cascade of N-cyclization and oxidative Heck reactions of o-alkynylanilines, has allowed the preparation o
- Denis,Franci,Altucci,Aurrecoechea,De Lera,lvarez
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p. 2800 - 2810
(2015/04/21)
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- AMIDE DERIVATIVES AND DRUGS
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The present invention provides an amide derivative represented by the following formula [1]: wherein n represents 0 or 1; X represents CR4 or N; Y represents CR6 or N; Z represents CR7 or N; R1 and R2 may be the same or different and each represents hydrogen, optionally substituted alkyl, acyl, optionally substituted aryl, or an optionally substituted aromatic heterocyclic group; R4, R5, R6 and R7 may be the same or different and each represents hydrogen, halogen, hydroxy, amino, alkyl, haloalkyl, alkoxy, monoalkylamino, dialkylamino, arylalkyl, cyano, or nitro; and R3 represents optionally substituted alkylamino, optionally substituted arylamino, or optionally substituted cyclic amino, or a pharmaceutically acceptable salt thereof, and a pharmaceutical composition comprising them as an active ingredient. The compound of the present invention is useful as a TGF-β inhibitor.
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- Condensed Heteroaromatic Ring Systems. XII. Synthesis of Indole Derivatives from Ethyl 2-Bromocarbanilates
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The palladium-catalyzed reaction of ethyl 2-bromocarbanilate with trimethylsilylacetylene yielded ethyl 2-(trimethylsilylethynyl)carbanilate, which was treated with sodium ethoxide to give indole.The carbanilates having a methyl or a bromo substituent were similarly transformed to corresponding indole derivatives.Furthermore, pyrrolo- and Pyrrolopyridines were synthesized by this method.Keywords---palladium-catalyzed reaction; trimethylsilylacetylene; ethyl 2-halocarbanilate; ethyl 2-halopyridinecarbamate; ethyl 2-(trimethylsilylethynyl)carbanylate; ethyl o-(trimethylsilylethynyl)pyridinecarbamate;indole;pyrrolopyridine
- Sakamoto, Takao,Kondo, Yoshinori,Iwashita, Shigeki,Yamanaka, Hiroshi
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p. 1823 - 1828
(2007/10/02)
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