Regioselective Multicomponent Synthesis of 2,4,6‐Trisubstituted Phenols from Fischer Alkynyl Carbene Complexes

López, Juan José Marín; Cruz, Fabiola N. de la; Flores-Conde, María Inés; Flores‐Álamo, Marcos; Delgado, Francisco; Tamariz, Joaquı́n; Vázquez, Miguel Á.

doi:10.1002/ejoc.201501211

Cited by 11 publications

(3 citation statements)

References 62 publications

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“…Even the simplest carbene complexes have exhibited great versatility [9]. The scope of the reaction increases in the event of the formation of an unsaturated system and is controlled by the type of substituents [10][11][12][13][14]. As a result, these organometallic complexes are capable of reacting with imines and many other molecules.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, investigating the behavior of Fischer carbenes in chemical reactions promoted by microwave energy is a relevant approach. In the methodologies developed by our group for the reaction of alkynyl and vinyl(alkoxy)carbene complexes under thermal conditions, substituents proved to play an important role in reactivity and selectivity during the synthesis of a variety of compounds, such as ortho-and para-quinones [39], phenols [12,40,41], furans, pyran-2-ones [42], 4-amino-1-azadienes [14], and pyrroles. The aim of the current contribution was to explore the reactivity of alkynyl(ethoxy)carbene complex 1 with benzylidene anilines 2a-p under microwave irradiation.…”

Section: Introductionmentioning

confidence: 99%

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Microwave-Assisted Reactivity of a Fischer Alkynyl Carbene Complex with Benzylidene Anilines

Delgado Reyes,

Feliciano,

Vazquez

et al. 2024

J. Mex. Chem. Soc.

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The reaction between the Fischer carbene complex (CO)5Cr=C(OEt)CºCPh and various benzylidene anilines RCH=NR1 was promoted by microwave irradiation, generating stable cross-conjugated metallahexatrienes in 45-70 % yield. Compared to conventional heating, the present conditions provided shorter reaction times with moderate yields. The geometrical configuration and the most stable conformation for each of the Fischer carbene complexes and their oxidation products were established by NMR and DFT analysis. The reaction mechanism was explored by DFT calculations of the potential energy surface, suggesting a 1,4-addition/ring closure/electrocyclic opening cascade process. Resumen. Se reporta la reactividad entre el carbeno de Fischer (CO)5Cr=C(OEt)CºCPh y las bencilidén anilinas, RCH=NR1, empleando irradiación de microondas. Los resultados indican que el calentamiento por microondas generó metalohexatrienos cruzados estables en rendimientos de 45-70 %, mostrando además, que los nuevos complejos se obtienen en tiempos de reacción más cortos y rendimientos moderados en comparación con las condiciones de calentamiento convencional. La configuración geométrica y la conformación más estable para los complejos carbénicos de Fischer y de sus derivados oxidados fueron establecidos por medio de RMN y DFT. La exploración de la superficie de energía potencial por cálculos DFT mostró que el proceso consistió en una reacción en cascada incluyendo una secuencia de adición-1,4, cierre de anillo y apertura electrocíclica.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Microwave-Assisted Reactivity of a Fischer Alkynyl Carbene Complex with Benzylidene Anilines

Delgado Reyes,

Feliciano,

Vazquez

et al. 2024

J. Mex. Chem. Soc.

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“…The Dötz benzannulation is driven by thermal energy for synthesizing phenols and its congeners from aromatic or vinylicalkoxy Fischer carbene complexes and functionalized alkynes as depicted in the Scheme . These phenol derivatives can further be transformed into the corresponding valuable quinones by simple oxidation method.…”

Section: Introductionmentioning

confidence: 99%

The Dötz Benzannulation Reaction: A Booming Methodology for Natural Product Synthesis

2020

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Since its finding in 1975, the Dötz benzannulation reaction has attracted a great attention of the scientific community as it permits the regio‐controlled construction of functionalised aromatic frameworks from acyclic precursors. In recent years, this beautifully simple yet much powerful technique for the formation of C−C bonds has opened‐up new possibilities in modern synthetic organic chemistry. In this Review, we report the developments in natural products synthesis by employing the Dötz benzannulation as a key transformation. Although, a flow of publications have witnessed a constant progress in this wonderful area of research, but to our best knowledge this is the first review which purely focuses on the applications of the Dötz benzannulation reaction in natural product synthesis. We are assured that this review will act as a promoter in amplifying the applications of the Dötz benzannulation in the domain of synthetic organic chemistry.

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Photoinduced Copper‐Catalyzed Cross‐Coupling of Acylsilanes with Heteroarenes via Bimetallic Relay

Zheng,

Li,

et al. 2024

Advanced Science

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The transition metal‐catalyzed direct coupling reactions involving electron‐rich Fischer carbene species are largely underdeveloped and remain a big challenge. Here, a direct coupling reaction of azoles and azine N‐oxides is reported with Fischer copper carbene species bearing an α‐siloxy group i, which can be in situ generated from acylsilanes catalytically under photoirradiation and redox‐neutral conditions. This coupling reaction between electron‐rich α‐siloxy Fischer Cu‐carbene species with hard carbanion nucleophiles may undergo a bimetallic relay process, which is confirmed by the kinetic analysis and in situ NMR analysis. This reaction features mild conditions and remarkable heterocycle compatibility. Notably, this protocol tolerates a series of azole or azine N‐oxide derivatives, including benzoxazole, benzothiazole, benzoimidazole, benzoisoxazole, oxazole, oxadiazole, triazolo[4,3‐a]pyridine, purine, caffeine, pyridine N‐oxide, quinoline N‐oxide, pyrazine N‐oxide, pyridazine N‐oxide, etc. The synthetic value of this approach is demonstrated by the efficient synthesis of a histamine h4 receptor ligand and a marketed drug carbinoxamine.

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Regioselective Multicomponent Synthesis of 2,4,6‐Trisubstituted Phenols from Fischer Alkynyl Carbene Complexes

Cited by 11 publications

References 62 publications

Microwave-Assisted Reactivity of a Fischer Alkynyl Carbene Complex with Benzylidene Anilines

Microwave-Assisted Reactivity of a Fischer Alkynyl Carbene Complex with Benzylidene Anilines

The Dötz Benzannulation Reaction: A Booming Methodology for Natural Product Synthesis

Photoinduced Copper‐Catalyzed Cross‐Coupling of Acylsilanes with Heteroarenes via Bimetallic Relay

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