Aerobic Visible-Light-Driven Borylation of Heteroarenes in a Gel Nanoreactor

Herrera-Luna, Jorge C.; Díaz, David Díaz; Abramov, Alex; Encinas, Susana; Jiménez, M. Consuelo; Pérez‐Ruiz, Raúl

doi:10.1021/acs.orglett.1c00451

Cited by 14 publications

(14 citation statements)

References 74 publications

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“…Recently, also the photolysis of heteroarene with bis‐(pinacolato)diboron (B 2 pin 2 ) and DIPEA was carried out in LBG and trans ‐Cy(UC 11 ) 2 ‐based organogels in aerated conditions (Scheme 35). [47] Interestingly, once again, the same reaction performed in aerated solution did not give rise to any product. In addition, the visible‐light‐driven thiophene borylation, firstly carried out as model reaction to set all reaction conditions, was considerably improved in the gel network in respect to the one performed in solution under inert atmosphere.…”

Section: Photocatalysismentioning

confidence: 74%

Catalysis in Supramolecular Systems: the Case of Gel Phases

et al. 2021

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Dedicated to Prof. Franco Cozzi in the occasion of his 70th birthday.Supramolecular gels are a fascinating class of materials, originated by the self-assembly of low molecular weight molecules. Underpinned by non-covalent interactions, they find application in a diverse range of fields. Among these, supramolecular gels can be considered as organized, nonconventional reaction media, able to influence reactivity in a radically different way, compared with what happens in solution. This short review will focus on this aspect, covering literature from 2010 onwards, addressing the application of supramolecular gels as reaction media. In particular, in the first section we explore organocatalytic reactions in gel phase, with wide synthetic relevance, such as aldol and Mannich reactions as well as Friedel Crafts or ester hydrolysis processes. Subsequently, focus is laid on metal-catalysed reactions, among which relevance is given to widely used reactions like crosscoupling and click reactions. Then, the final sections describe the use of supramolecular gels as reaction media for photoand biocatalysed processes.

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Section: Photocatalysismentioning

confidence: 74%

Catalysis in Supramolecular Systems: the Case of Gel Phases

et al. 2021

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Section: Introductionmentioning

confidence: 99%

“…Supramolecular viscoelastic gels 50 fulfill properly the requirements to act as a photonanoreactor-like system, and investigations of air-sensitive photochemical reactions have been successfully achieved in such microenvironments. 51,52 With this background, we describe herein our endeavors toward the aerobic visible-light-mediated phosphorylation of five-membered heteroarenes in gel-based nanoreactor that, as far as we are aware, remains unexplored (Scheme 2).…”

Section: ■ Introductionmentioning

confidence: 99%

“…In this sense, research groups have been devoted to developing artificial photonanoreactors based on low-molecular-weight (LMW) molecules self-assembled by noncovalent interactions (e.g., hydrogen bonding, van de Waals, charge transfer, dipolar, π–π stacking) , in order to access otherwise slow or forbidden pathways and achieve high selectivity under mild conditions. Supramolecular viscoelastic gels fulfill properly the requirements to act as a photonanoreactor-like system, and investigations of air-sensitive photochemical reactions have been successfully achieved in such microenvironments. , …”

Section: Introductionmentioning

confidence: 99%

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Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis

Herrera-Luna

Díaz

Jiménez

et al. 2021

ACS Appl. Mater. Interfaces

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A new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes with excellent yields using dichromatic photoredox catalysis in a gel-based nanoreactor is described here. The procedure involves visible aerobic irradiation (cold white LEDs) of a mixture containing the heteroarene halide, trisubstituted phospite, N , N -diisopropylethylamine (DIPEA) as sacrificial agent, and catalytic amounts of 9,10-dicyanoanthracene ( DCA ) in the presence of an adequate gelator, which permits a faster process than at the homogeneous phase. The methodology, which operates by a consecutive photoinduced electron transfer (ConPET) mechanism, has been successfully applied to the straightforward and clean synthesis of a number of different heteroarene (furan, thiophene, selenophene, pyrrole, oxazole, or thioxazole) phosphonates, extending to the late-stage phosphonylation of the anticoagulant rivaroxaban. Strategically, employment of cold white light is critical since it provides both selective wavelengths for exciting first DCA (blue region) and subsequently its corresponding radical anion DCA •– (green region). The resultant strongly reducing excited agent DCA •– * is capable of even activate five-membered heteroarene halides (Br, Cl) with high reduction potentials (∼−2.7 V) to effect the C(sp 2 )–P bond formation. Spectroscopic and thermodynamic studies have supported the proposed reaction mechanism. Interestingly, the rate of product formation has been clearly enhanced in gel media because reactants can be presumably localized not only in the solvent pools but also through to the fibers of the viscoelastic gel network. This has been confirmed by field-emission scanning electron microscopy images where a marked densification of the network has been observed, modifying its fibrillary morphology. Finally, rheological measurements have shown the resistance of the gel network to the incorporation of the reactants and the formation of the desired products.

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“…So, to overcome this difficulty the author introduced another photocatalyst-free visible light-induced approach for the borylation of heteroaryl chlorides and bromides (Scheme 6e). [46] The author utilizes N, N'bis(octadecyl)-L-Boc-glutamic diamide self-assembled gel nanoreactor as the reaction media which offers a suitable microenvironment and allows the reaction to happen under aerobic conditions. Under the optimized reaction conditions, a wide range of thiophene, furan, pyrrole, and selenophene halides were well tolerated and the corresponding borylated products were obtained in good to excellent yields.…”

Section: Through Light-induced Borylationmentioning

confidence: 99%

Transition‐Metal‐Free Heterocyclic Carbon‐Boron Bond Formation

Hazra

Mahato

Das

et al. 2022

Chemistry A European J

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Heteroaryl boronic acids and esters are extremely important and valuable intermediates because of their wide application in the synthesis of marketed drugs and bioactive compounds. Over the last couple of decades, the construction of highly important heteroaryl carbon‐boron bonds has created huge attention. The transition‐metal‐free protocols are more green, less sensitive to air and moisture, and also economically advantageous over the transition‐metal‐based protocols. The transition‐metal‐free C−H borylation of heteroarenes and C−X (X=halogen) borylation of heteroaryl halides represents an excellent approach for their synthesis. Also, various cyclization and alkyne activation protocols have been recently established for their synthesis. The goal of this review article is to summarize the existing literature and the current state of the art for transition‐metal‐free synthesis of heteroaryl boronic acid and esters.

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Aerobic Visible-Light-Driven Borylation of Heteroarenes in a Gel Nanoreactor

Cited by 14 publications

References 74 publications

Catalysis in Supramolecular Systems: the Case of Gel Phases

Catalysis in Supramolecular Systems: the Case of Gel Phases

Highly Efficient Production of Heteroarene Phosphonates by Dichromatic Photoredox Catalysis

Transition‐Metal‐Free Heterocyclic Carbon‐Boron Bond Formation

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