Functionalization of indole at C-5 or C-7 via palladium-catalysed double carbonylation. A facile synthesis of indole ketocarboxamides and carboxamide dimers

Takács, Attila; Marosvölgyi-Haskó, Diána; Kabak-Solt, Zsuzsanna; Damas, Liliana; Rodrigues, Fábio M. S.; Carrilho, Rui M. B.; Piñeiro, Marta; Pereira, Mariette M.; Kollár, László

doi:10.1016/j.tet.2015.11.007

Cited by 18 publications

(18 citation statements)

References 26 publications

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“…Under these conditions, a full conversion in 24 h was observed by 1 H NMR analysis of the crude reaction mixture. However, besides a mixture of the expected carboxamide and ketocarboxamide products, the formation of N , N -dimethyl-1 H -indole-7-carboxamide ( 2.1 ) was observed as a side-product (15% isolated yield), which results from DMF in situ decomposition [ 34 , 54 ]. This problem was overcome by replacing DMF with toluene in the following experiments.…”

Section: Resultsmentioning

confidence: 99%

“…This problem was overcome by replacing DMF with toluene in the following experiments. Nevertheless, using toluene under the same reaction conditions (10 bar CO, 100°C, 0.5 eq diamine), the target cyclized product 2a was barely formed, with the dicarboxamide derivative 3a being identified as the major product [ 34 ]. The reaction was then performed using an excess of diamine with respect to the iodoindole substrate ( 1 / a molar ratio = 1 : 1.5).…”

Section: Resultsmentioning

confidence: 99%

“…More recently, we reported the first Pd-catalysed double carbonylation of 5-iodo- and 7-iodoindole using monoamines as the nucleophiles, which allowed the synthesis of a new family of indole-based ketocarboxamides [ 34 ]. We also described the aminocarbonylation of 7-iodoindole in the presence of diamines [ 34 ], leading to indole-based mono- and/or dicarboxamides ( scheme 1 a ).

Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

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A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis- N -heterocycles: rationalization by electronic structure calculations

et al. 2018

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An unprecedented palladium-catalysed sequential aminocarbonylation/cyclization synthetic strategy, using carbon monoxide and structurally different aliphatic diamines as N-nucleophiles, gives access, in one pot, to a new family of indole-based N-heterocyclic derivatives (hydropyrazinones, benzodiazepinones and hydroquinoxalines). Optimization of the reaction conditions towards double carbonylation (PCO = 30 bar, T = 80°C, iodoindole/diamine ratio = 1 : 1.5, toluene as solvent) allowed the target cyclic products, which are formed in situ via intramolecular cyclization of the ketocarboxamide intermediates, to be obtained through a nucleophilic addition/elimination reaction with the pendant terminal amine groups. The structure of the diamine nucleophile was revealed to affect the reaction's selectivity, with the best yields for the cyclic products being obtained in the presence of (1S,2S)-(+)-cyclohexane-1,2-diamine (a) as the nucleophile, using either 5- or 7-iodoindole as the substrate. The reaction's selectivity was rationalized based on electronic structure calculations, which explain the effect of the diamine structure on the predominant formation of the cyclic products.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

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A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis- N -heterocycles: rationalization by electronic structure calculations

et al. 2018

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“…16 In the presence of diamines, palladium-catalyzed carbonylation of 7-iodoindole under 10 atm CO pressure led mainly to carboxamide dimers 10 (Scheme 6). 17 -Ketoamides 12a,j-z,aa-ae were the major compounds obtained from the Pd-catalyzed reaction of unprotected iodoindoles using 40 atm CO pressure and a variety of amines, except aniline. The low basicity of aniline led mainly to the monocarbonylation coupling products 7 (Scheme 7).…”

Section: Introductionmentioning

confidence: 99%

“…The low basicity of aniline led mainly to the monocarbonylation coupling products 7 (Scheme 7). 17 It is interesting to point out that the bro-moaryl moiety of 5-bromo-7-iodoindole remained intact under the conditions used (Scheme 7).…”

Section: Introductionmentioning

confidence: 99%

Carbonylated Indoles from PdII-Catalyzed Intermolecular Reactions of Indolyl Cores

Bras¹,

Мuzart

2019

Synthesis

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This review summarizes palladium-catalyzed carbonylation, transmetalation, and cross-coupling reactions that lead to carbonylated indoles from indoles and indolyl compounds. Special attention is drawn to procedures involving the C(sp2)–H substitution of free (NH)-indoles or (N-substituted)-indoles. Proposed mechanisms are described with, in some cases, personal comments.1 Introduction2 Carbonylative Reactions2.1 Indolyl Halides as Starting Substrates2.2 Indolyl Iodides as Intermediates2.3 Indolylborates as Intermediates2.4 C(sp2)–H Reactions2.4.1 Carboxylation2.4.2 Carbonylative Alkoxylation2.4.3 Carbonylative Arylation2.4.4 Carbonylative Alkenylation2.4.5 Carbonylative Alkylation2.4.6 Double Carbonylation3 Cross-Coupling of Stannyl- or Mercurioindoles4 Cross-Coupling of Indoles4.1 Aldehydes4.2 Alcohols4.3 α-Diketones4.4 α-Oxo Esters4.5 α-Oxocarboxylic Acids4.6 Nitriles4.7 Isocyanides4.8 Isothiocyanates and Isocyanates4.9 α-Aminocarbonyl Compounds4.10 Vinyl Ethers or Vinyl Amides4.11 Toluene and Substituted Toluenes4.12 Bromodichloromethane5 Conclusion

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Double Carbonylation Reactions: Overview and Recent Advances

Das

Bhanage

2020

Adv Synth Catal

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The compounds like amides, carbamates, oxamates, oxamides, α‐keto amides, diketones, esters, ureas, etc. find extensive applications in pharmaceuticals, agrochemicals and organic synthesis. The classical syntheses of these compounds often involve cumbersome routes involving toxic chemicals. The carbonylation reactions such as aminocarbonylation, alkoxycarbonylation, oxidative carbonylation and double carbonylation deliver as an efficient and attractive alternative to the conventional synthetic routes even at industrial scales. The catalytic single carbonylation reactions are extensively studied, however, catalytic double carbonylation reactions are not explored for several potential applications. This review covers literature on the use of different types of catalysts involving various metals like Pd, Cu, Fe, Co, Rh and Ni for double carbonylation reactions along with the chemistry of associated ligands. It also covers double carbonylation with different types of substrates with the discussion related to the mechanism of formation of mono‐ and di‐carbonylation products. The notable introduction of several CO‐surrogates and exploration of their efficiency have solved the problems related to the toxicity of CO. CO‐surrogates used for double carbonylation reactions are also discussed.magnified image

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Functionalization of indole at C-5 or C-7 via palladium-catalysed double carbonylation. A facile synthesis of indole ketocarboxamides and carboxamide dimers

Cited by 18 publications

References 26 publications

A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis- N -heterocycles: rationalization by electronic structure calculations

A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis- N -heterocycles: rationalization by electronic structure calculations

Carbonylated Indoles from PdII-Catalyzed Intermolecular Reactions of Indolyl Cores

Double Carbonylation Reactions: Overview and Recent Advances

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