Selective synthesis of trisubstituted pyrroles through the reactions of alkynyl Fischer carbene complexes with oxazolones

López, Juan José Marín; Velazco-Cabral, Iván; Rodríguez-deLeón, Eloy; Gómez, Clarisa Villegas; Delgado, Francisco; Tamariz, Joaquı́n; Arrieta, Ana; Cossío, Fernando P.; Vázquez, Miguel Á.

doi:10.1039/c9ob02411e

Cited by 11 publications

(11 citation statements)

References 42 publications

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“…Pyrroles were obtained under previously reported conditions [33] . In this synthesis, the addition of 0.15 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…General procedures for pyrroles 3 a-e: Compounds 3 a-e were synthesized by the previously reported methodology. [33] In a 100 mL round bottom flask, Fischer alkynylcarbenes 1 a-c (2.14 mmol), and oxazolones 2 a-c (4.28 mmol) were added. The flask was sealed and purged with nitrogen.…”

Section: Synthetic Methodsmentioning

confidence: 99%

“…The retrosynthetic route to generate the polysubstituted BODIPYs is presented in Scheme 1. Our strategy is based on the use of different Fischer alkynylcarbenes 1 a-c and oxazolones 2 a-c to obtain the pyrroles 3 a-e. [33] The resulting pyrroles were then treated with different aldehydes in acid medium to generate the dipyrromethanes 5 a-m. Finally, under Lyndsey conditions, [34] the dipyrromethanes were oxidized, and subsequently, the addition of N,N-diisopropylethylamine (DIPEA) and boron trifluoride diethyl etherate (BF 3 •OEt 2 ) gave rise to the target symmetrical BODIPYs 6 a-l.…”

Section: Organic Synthesismentioning

confidence: 99%

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Synthesis of Polysubstituted Symmetrical BODIPYs via Fischer Carbene Complexes: Theoretical, Photophysical and Electrochemical Evaluation

Vázquez

Velazco-Cabral

Flores‐Álamo

et al. 2022

Chemistry A European J

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A series of new symmetrical highly substituted BODIPYs 6 a–l was synthesized through a prefunctionalization approach in 35 %–89 % yields from the pyrrole core. This strategy allowed modulation of the substituents at the different positions based on the choice of Fischer's alkynyl carbenes, oxazolones and aldehydes used as precursors. The substituent variation at positions 2, 6, 3 and 5 had the greatest effect on the modulation of their photophysical properties such as absorption (λabs) and emission (λem) wavelengths, extinction coefficient (ϵ), quantum yields (ϕ), Stokes shifts (Δν), fluorescence decay, radiative (krad) and non‐radiative (knr) constants and the CIE 1931 coordinates. Theoretical calculations allowed to corroborate the effect of the substituents of meso‐position on the modification of the dihedral angles. Cyclic voltammetry studies revealed that the BODIPY series presents similar redox potential behavior, being electrochemically active even in successive cycles, which suggests that transport by diffusion is the dominant process.

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“…Pyrroles were obtained under previously reported conditions [33] . In this synthesis, the addition of 0.15 equiv.…”

Section: Resultsmentioning

confidence: 99%

Section: Synthetic Methodsmentioning

confidence: 99%

Section: Organic Synthesismentioning

confidence: 99%

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Synthesis of Polysubstituted Symmetrical BODIPYs via Fischer Carbene Complexes: Theoretical, Photophysical and Electrochemical Evaluation

Vázquez

Velazco-Cabral

Flores‐Álamo

et al. 2022

Chemistry A European J

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“…A new method for synthesis of novel trisubstituted 1H‐pyrroles 345 a – q via 1,3‐dipolar cycloaddition of trifluoromethyloxazolones 343 a – d with alkynes 342 a – h was presented by López and collegues [107] . This reaction include unexpected CF 3 group elimination process.…”

Section: Cycloaddition Reactionsmentioning

confidence: 99%

Recent Advances for the Synthesis of N‐Unsubstituted Pyrroles

et al. 2021

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Pyrroles are an interesting class of heterocyclic compounds due to their widespread use both in medical chemistry and in the chemistry of new materials. Search and development of new effective methods for the synthesis of the pyrrole ring is an urgent task. Along with this, the systematization of already known synthesis methods is an equally important task. Herein, we focused on the results of the synthesis of NH‐pyrroles that have been obtained since 2015.

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“…FCCs containing group VI transition metals [29,31–33] are very versatile in cyclization and cycloaddition reactions with an α,β‐unsaturated system under different conditions, [29] resulting in carbocycles, [34–39] heterocycles [29,40–43] and a diversity of other compounds. Chromium carbene complexes have shown particularly suitable reactivity, compared to the greater stability of tungsten and the extreme reactivity of molybdenum complexes [44–47] .…”

Section: Introductionmentioning

confidence: 99%

Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions

Feliciano

Vázquez

Benítez‐Puebla

et al. 2021

Chemistry A European J

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The structure of Fischer carbene complexes (FCCs) is electron deficient. If bearing an α,β‐unsaturated system, it can generate a wide variety of compounds by undergoing many different transformations, including higher‐order cycloadditions. The latter are described as pericyclic reactions in which more than six electrons participate. These reactions have been employed in various areas of organic synthesis, resulting in highly selective compounds with a broad range of scaffolds. The first studies on higher‐order cycloadditions involving FCCs frequently yielded competing byproducts. Many groups have attempted to increase selectivity by exploring distinct reaction conditions, reagents and co‐catalysts (e. g., metal‐mediated cycloadditions). The present review is the first to focus exclusively on using higher‐order cycloadditions involving FCCs to synthesize carbocycles and heterocycles. Based on two decades of reports, an analysis is made of the main aspects of the mechanisms proposed for higher‐order cycloadditions and the structural diversity obtained by the substituent effect.

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Selective synthesis of trisubstituted pyrroles through the reactions of alkynyl Fischer carbene complexes with oxazolones

Abstract: The unexpected reactivity of fluorinated oxazolones with alkynyl Fischer carbenes is reported. The loss of the –CF3 and a cascade process involving nucleophilic additions were observed.

Cited by 11 publications

References 42 publications

Synthesis of Polysubstituted Symmetrical BODIPYs via Fischer Carbene Complexes: Theoretical, Photophysical and Electrochemical Evaluation

Synthesis of Polysubstituted Symmetrical BODIPYs via Fischer Carbene Complexes: Theoretical, Photophysical and Electrochemical Evaluation

Recent Advances for the Synthesis of N‐Unsubstituted Pyrroles

Fischer Carbene Complexes: A Glance at Two Decades of Research on Higher‐Order Cycloaddition Reactions

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