An ultrastable olefin-linked covalent organic framework for photocatalytic decarboxylative alkylations under highly acidic conditions

Tian, Mingzhen; Wang, Yichun; Bu, Xiubin; Wang, Yichen; Yang, Xiaobo

doi:10.1039/d1cy00293g

Cited by 40 publications

(35 citation statements)

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“…Alkylation of quinoxalin-2(1H)-ones and related heterocycles (e.g., isoquinolines, quinolines) via photocatalytic decarboxylative generation of carbon-centered radicals have also been explored recently by Yang and co-workers, where they tested four imine-linked 2D-COFs and one olefin-linked COF (2D-COF-2) as heterogeneous photocatalysts. 58 The proposed reaction mechanism occurs similarly to that described in Scheme 21b, whereby the generation of carboncentered radicals occurs upon reduction of N-hydroxyphthalimide (NHPI) esters (E = −1.20 V vs SCE) by the 2D-COF-2-CB (E = −1.40 V vs SCE) which delivers the desired alkyl Other Relevant Reactions. The hydrazone-based COF, TFB-COF, has also been employed by Yang and co-workers as visible-light photocatalyst for cyclization reactions, namely, (i) radical addition-cyclization of 2-aryl phenyl isocyanides for the synthesis of 6-substituted phenanthridines, 52 and (ii) the oxidative construction of N−S bond for the preparation of 1,2,4-thiadiazoles (Scheme 22).…”

Section: ■ Introductionmentioning

confidence: 90%

Light-Induced Organic Transformations by Covalent Organic Frameworks as Reticular Platforms for Selective Photosynthesis

Costa

Vega‐Peñaloza

Cognigni

et al. 2021

ACS Sustainable Chem. Eng.

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Photoassisted synthesis of value-added organic products has developed greatly in the last decades in response to the pressing need for a transition toward sustainable processes and renewable energy. One of the formidable challenges of the light-induced chemical steps is provided by the control of the catalytic efficiency and selectivity under photocatalytic conditions. An attractive perspective is foreseen by triggering the photoreaction events in confined spaces, wherein light harvesting and photocatalytic units are framed into functional architectures. Division of tasks among specialized compartments responds to a bioinspired strategy with the final aim to orchestrate the rate of concurrent and sequential events, to maximize performance while directing the reaction selectivity. Covalent organic frameworks (COFs) are a class of emerging materials that can meet these requirements, with the potential to bridge the existing gap between molecular and heterogeneous photocatalysis. Here, a rich pool of molecular building blocks and chemical linkages is available to afford crystalline porous solids with tailored photophysical properties emerging from the interconnected COF structure walls, while catalytic cofactors can be provided by engineering of the pore surface. In this Perspective, we highlight recent developments where COFs have been successfully employed as photocatalysts for selective organic transformations. The relationship between the COF reticular structure and its photocatalytic behavior is discussed, in terms of the light-conversion pathways and photoredox events, including electron and/or energy transfer mechanisms. The possible role of confinement effects, intrinsic in long-range order porous COF materials, remains largely unexplored in photocatalytic applications. New progress is expected to arise from close interdisciplinary cooperation involving synthetic chemistry and materials science communities.

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Section: ■ Introductionmentioning

confidence: 90%

Light-Induced Organic Transformations by Covalent Organic Frameworks as Reticular Platforms for Selective Photosynthesis

Costa

Vega‐Peñaloza

Cognigni

et al. 2021

ACS Sustainable Chem. Eng.

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“…Tian et al [83] have utilized olefin-linked two-dimensional covalent organic framework 2D-COF-2 (Figure 16) for the photocatalytic decarboxylative alkylation of diverse heterocycles (like quinolines, isoquinolines, quinoxaline-2(1H)-ones etc.) with Nhydroxyphthalimide (NHPI) esters (Scheme 5).…”

Section: Photocatalytic Decarboxylative Alkylationmentioning

confidence: 99%

Evolving Trends for C−C Bond Formation Using Functionalized Covalent Organic Frameworks as Heterogeneous Catalysts

Pasricha

Chaudhary²,

Srivastava

2022

ChemistrySelect

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Covalent organic frameworks (COFs), also called “Organic Zeolites,” are crystalline porous organic polymers with robust and pre‐designable architecture and high crystallinity. They can be structurally controlled and functionally managed, due to the availability of diverse organic functionalities, covalent linkages and topologies. The current review briefly outlines their design strategies and comprehensively discusses their applications in the carbon‐carbon bond formation reactions. The reactivity of COF‐based catalysts with their homogeneous counterparts, catalyst stability, role of matrix, tailored organocatalysts and substituent effect on the reaction parameters, chemo‐/stereo‐/regioselectivity, shape/size selectivity are also discussed. Finally, the challenges and future prospects of functionalized COF‐based catalysts are discussed. These discussions will provide a better understanding of the role of COF‐based catalysts in the C−C bond formation and will also open doors to the design and synthesis of more robust, sustainable and benign catalytic systems, which might play a key role in organic synthesis and catalysis.

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“…[10] The dimensional increase from linear conjugated polymers to 2D CPs is of particular interest due to the faster-evolving bandgaps [11] and enhanced chemical and physical properties, including chemical and thermal stabilities, and increased charge carrier transport compared to their linear counterparts. [12][13][14][15][16] Due to the atomically precise integration of (functional) building blocks into ordered and porous sp 2 -carbon-conjugated structures with π-delocalization in two dimensions, vinylenelinked 2D CPs have been demonstrated as an efficient light emitter, [17,18] artificial photosystem I, [19] in catalysis, [20,21] sensors, [22] energy storage, [23,24] and conversion. [25,26] Previously, the Knoevenagel [10,16,18,23,25,27] and other aldol-type polycondensations [20,24,28,29] have been employed for the synthesis of crystalline (cyano)-vinylene-linked 2D CPs.…”

Section: Introductionmentioning

confidence: 99%

“…Due to the atomically precise integration of (functional) building blocks into ordered and porous sp 2 ‐carbon‐conjugated structures with π‐delocalization in two dimensions, vinylene‐linked 2D CPs have been demonstrated as an efficient light emitter, [17,18] artificial photosystem I, [19] in catalysis, [20,21] sensors, [22] energy storage, [23,24] and conversion [25,26] . Previously, the Knoevenagel [10,16,18,23,25,27] and other aldol‐type polycondensations [20,24,28,29] have been employed for the synthesis of crystalline (cyano)‐vinylene‐linked 2D CPs.…”

Section: Introductionmentioning

confidence: 99%

Control of Crystallinity of Vinylene‐Linked Two‐Dimensional Conjugated Polymers by Rational Monomer Design

Pastoetter

Liu

Addicoat

et al. 2022

Chemistry A European J

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The interest in two-dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene-linked 2D CPs with fully in-plane sp 2carbon-conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner-Wadsworth-Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene-linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D-poly(phenylenequinoxaline-vinylene)s (2D-PPQVs) and 2D-poly(phenylenevinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible CÀ C single bond formation.

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An ultrastable olefin-linked covalent organic framework for photocatalytic decarboxylative alkylations under highly acidic conditions

Abstract: The application of two-dimensional covalent organic frameworks (2D-COFs) as photoredox catalysts offers a sustainable alternative for visible-light-driven organic transformations. However, under highly complicated organic reaction conditions, maintaining their basic structure...

Cited by 40 publications

References 95 publications

Light-Induced Organic Transformations by Covalent Organic Frameworks as Reticular Platforms for Selective Photosynthesis

Light-Induced Organic Transformations by Covalent Organic Frameworks as Reticular Platforms for Selective Photosynthesis

Evolving Trends for C−C Bond Formation Using Functionalized Covalent Organic Frameworks as Heterogeneous Catalysts

Control of Crystallinity of Vinylene‐Linked Two‐Dimensional Conjugated Polymers by Rational Monomer Design

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