Regiodivergent synthesis of pyrazino-indolines <i>vs.</i> triazocines <i>via</i> α-imino carbenes addition to imidazolidines

Guarnieri‐Ibáñez, Alejandro; Aguirre, Adiran de; Besnard, Céline; Poblador‐Bahamonde, Amalia I.; Lacour, Jérôme

doi:10.1039/d0sc05725h

Cited by 21 publications

(18 citation statements)

References 88 publications

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“…First, the nature of the metal catalyst was investigated, 2 switching from copper to dirhodium and cyclopentadienyl ruthenium complexes ( entries 3 and 4 ) while decreasing the temperature to 60 °C with these more reactive decomposition catalysts. Using Rh 2 (OAc) 4 (1 mol‐%), [45] a yield of 37 % was obtained, while decomposition with [CpRu(MeCN)] 3 PF 6 (2.5 mol‐%) [46,47] led to a drastic improvement and a corresponding yield of 80 %. Selecting the [CpRu] complex for further experiments, the influence of the negative counterion was investigated, switching from PF 6 − to the large, lipophilic and less coordinating BAr F − anion [42] .…”

Section: Resultsmentioning

confidence: 99%

Spirocyclic Amide Acetal Synthesis by [CpRu]‐Catalyzed Condensations of α‐Diazo‐β‐Ketoesters with γ‐Lactams

Pertschi

Brun

Aguirre

et al. 2021

Helvetica Chimica Acta

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The synthesis of spirocyclic amide acetals (33–93 %) has been achieved through Ru(II)‐catalyzed condensations of N‐carbamate protected pyrrolidinones with metal carbenes derived from α‐diazo‐β‐ketoesters. Thanks to the mildness of the diazo decomposition conditions induced by a 1 : 1 combination of [CpRu(MeCN)3][BArF] and 1,10‐phenanthroline, the formation of the sensitive products is possible. Full characterization of this carbonyl‐ylide mediated process is provided by DFT calculations.

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Section: Resultsmentioning

confidence: 99%

Spirocyclic Amide Acetal Synthesis by [CpRu]‐Catalyzed Condensations of α‐Diazo‐β‐Ketoesters with γ‐Lactams

Pertschi

Brun

Aguirre

et al. 2021

Helvetica Chimica Acta

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“…Very recently, the same group reported the single-step preparation of hexahydropyrazinoindoles 92.3 through a Rh(II)-catalyzed cascade reaction of N -sulfonyl-1,2,3-triazoles 92.1 and imidazolidines 92.2 (Scheme ). This cascade also involves sequential carbene generation, ylide formation, [1,2]-Stevens, and Friedel–Crafts reactions. Interestingly, treatment of triazoles 92.6 with unsymmetrical imidazolidines 92.7 led to the unprecedented formation of eight-membered hexahydro-1,3,6-triazocines 92.8 , in contrast to the symmetrical imidazolidines.…”

Section: Denitrogenative Transformations Of Triazolesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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Readily accessible and shelf-stable 1,2,3-triazole and its analogues such as pyridotriazole, triazoloindole, benzotriazole, and thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These ring-opened isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding metal carbenoids with extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access to a realm of N-containing complex structural motifs of biological importance through denitrogenative transformations such as transannulations, insertions, ylide formation, and rearrangements by trapping of the metal carbenoids with a diverse range of coupling partners (e.g., alkenes, alkynes, nitriles, carbo/heterocycles, X–H/C–X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged as efficient surrogates of diazo compounds for the generation of reactive metal carbenoids during the past decades. In this comprehensive review, we aim to discuss in detail the remarkable advancement in their synthesis and synthetic applications.

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“…Guinchard et al also reported an Au(I)-catalyzed Pictet–Spengler reaction to prepare a variety of complex heterocyclic compounds including tetrahydro-pyrazinoindoles with good yields ranging from 43 to 93% [ 21 ]. In 2021, Lacour et al reported that N -sulfonyltriazoles 26 and imidazolines 27 reacted under rhodium catalysis to give a variety of hexahydro-pyrazinoindoles 28 with excellent yields easily transformed in tetrahydropyrazinoindoles 29 after a welcome rearrangement in triflic acid TfOH [ 22 ]. Ghorai et al reported in 2018 of an elegant synthesis of 1,3-disubstituted 1,2,3,4-tetrahydropyrazino[1,2- a ]indoles 32 with excellent stereoselectivity (de, ee >99%) via base-mediated ring opening of chiral aziridines 31 with skatoles 30 followed by BF 3 -OEt 2 catalyzed Pictet–Spengler reaction [ 23 ].…”

Section: Pyrazinoindoles A: Synthesis and Biological Propertiesmentioning

confidence: 99%

Synthesis and Biological Activities of Pyrazino[1,2-a]indole and Pyrazino[1,2-a]indol-1-one Derivatives

et al. 2021

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This review concerns the synthesis and biological activities of pyrazino[1,2-a]indoles and pyrazino[1,2-a]indol-1-ones reported since 1997 and the discovery of biological activity of pyrazinoindole derivatives. In the first part, we first presented the synthetic routes that have been reported from a methodological point of view to access the pyrazinoindole unit according to cyclization reactions using or not using metal catalysts. Then, syntheses and neuropsychiatric, auto-immune, anti-infectious and anti-cancer properties of pyrazinoindoles were detailed. In the second part, we first reported the main accesses to pyrazinoindol-1-one substrates according to Michael reactions, metal-catalyzed and metal-free cyclization reactions. The syntheses and anti-cancer, anti-infectious, anti-allergenic and neuropsychiatric properties of pyrazinoindolones were next described and discussed.

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Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines

Abstract: Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines. Under dirhodium catalysis, α-imino carbenes were generated and formed nitrogen ylide intermediates that, after subsequent aminal opening, afforded...

Cited by 21 publications

References 88 publications

Spirocyclic Amide Acetal Synthesis by [CpRu]‐Catalyzed Condensations of α‐Diazo‐β‐Ketoesters with γ‐Lactams

Spirocyclic Amide Acetal Synthesis by [CpRu]‐Catalyzed Condensations of α‐Diazo‐β‐Ketoesters with γ‐Lactams

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

Synthesis and Biological Activities of Pyrazino[1,2-a]indole and Pyrazino[1,2-a]indol-1-one Derivatives

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