Amidation, Esterification, and Thioesterification of a Carboxyl‐Functionalized Covalent Organic Framework

Guo, Lei; Jia, Shang; Diercks, Christian S.; Yang, Xuejing; Alshmimri, Sultan A.; Yaghi, Omar M.

doi:10.1002/ange.201912579

Cited by 30 publications

(18 citation statements)

References 32 publications

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“…Furthermore, the fact that the precursor for PSM (i.e., the hierarchically porous MOF decorated with anhydride groups) can be easily prepared from simple low-cost carboxylate-based MOFs via thermolysis in a controlled fashion and that, in addition to MIL-121, many important MOFs either have or can be easily functionalized to form free carboxylic acid groups make this new PSM method widely applicable for diverse applications. Looking forward, covalent organic frameworks (COFs) can be functionalized via carboxylic groups, 49,50 which suggests that the protocol described here can be expanded to include PSM of COFs and other related porous organic polymers.…”

Section: Discussionmentioning

confidence: 99%

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

et al. 2020

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Metal–organic frameworks (MOFs) are important porous materials. Post-synthetic modification (PSM) of MOFs via the pendant groups or secondary functional groups of organic linkers has been widely used to introduce new or enhance existing properties of MOFs for various practical applications. In this work, we have constructed, for the first time, a novel platform for PSM of MOFs by introducing an anhydride functional group into a hierarchically porous MOF (MIL-121) as an effective anchor. We have demonstrated that the combination of the high reactivity of anhydride and hierarchical porosity makes this protocol particularly novel and important, as it led to excellent opportunities of incorporating not only a wide variety of organic molecules with different sizes and chemical nature but also the noble metal complexes in MOFs. Specifically, we show that the anhydride group decorated in the MOF exhibits a high reactivity toward covalently binding 10 different guest molecules including alcohols, amines, thiols, and noble metal (Pt(II)/Pt(IV)) complexes, whereas the hierarchical pores created in the MOF allow the incorporation of guest species varying in size from methanol to larger molecules such as polyaromatic amines. This novel approach provides the community with a new avenue to prepare MOF-based materials for targeted applications. To illustrate this point, we furnish an example of using this new platform to prepare a Pt-based electrocatalyst which shows excellent catalytic activity toward the oxygen reduction reaction (ORR), a pivotal half-reaction in hydrogen–oxygen fuel cells and other energy storage and conversion devices.

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Section: Discussionmentioning

confidence: 99%

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

et al. 2020

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“…The synthesis of amides is among the most important reactions in organic chemistry and biochemistry because of the widespread occurrence of amides in pharmaceuticals, peptides, biologically active compounds, industrial polymers, detergents, and lubricants [ 1 , 2 , 3 , 4 , 5 , 6 ]. Consequently, many different physical [ 7 ] and chemical protocols have been developed for the synthesis of amides by dehydro-condensation of a carboxylic acid and an amine [ 8 , 9 , 10 , 11 , 12 , 13 ]. Catalytic routes for the preparation of amides have also been reported with the intent to increase atom efficiency of the process [ 2 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis

et al. 2021

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Conventional methods employed today for the synthesis of amides often lack of economic and environmental sustainability. Triazine-derived quaternary ammonium salts, e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM(Cl)), emerged as promising dehydro-condensation agents for amide synthesis, although suffering of limited stability and high costs. In the present work, a simple protocol for the synthesis of amides mediated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and a tert-amine has been described and data are compared to DMTMM(Cl) and other CDMT-derived quaternary ammonium salts (DMT-Ams(X), X: Cl− or ClO4−). Different tert-amines (Ams) were tested for the synthesis of various DMT-Ams(Cl), but only DMTMM(Cl) could be isolated and employed for dehydro-condensation reactions, while all CDMT/tert-amine systems tested were efficient as dehydro-condensation agents. Interestingly, in best reaction conditions, CDMT and 1,4-dimethylpiperazine gave N-phenethyl benzamide in 93% yield in 15 min, with up to half the amount of tert-amine consumption. The efficiency of CDMT/tert-amine was further compared to more stable triazine quaternary ammonium salts having a perchlorate counter anion (DMT-Ams(ClO4)). Overall CDMT/tert-amine systems appear to be a viable and more economical alternative to most dehydro-condensation agents employed today.

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“…[41] But excellent properties are not only limited to those related with the backbone constituents, because COFs can be further functionalized postsynthetically. [42] In general, COFs can be classified attending to two structural parameters: type and topology of formed bonds. [33]…”

Section: Introductionmentioning

confidence: 99%

Microwave‐Assisted Synthesis of Covalent Organic Frameworks: A Review

et al. 2020

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Covalent organic frameworks (COFs) are relatively recent materials. They have received great attention due to their interesting properties. However, the application of microwaves in their synthesis, despite its advantages such as faster and more reproducible processes, is a minority. Herein, a comprehensive compilation of the research results published in the microwave‐assisted synthesis (MAS) of COFs is presented. This review includes articles of 2D and 3D COFs prepared using microwaves as source of energy. The articles have been classified depending on the functional groups including boronate ester, imines, enamines, azines, and triazines, among others. It compiles the main parameters of synthesis and characteristics of the materials together with some general issues related with COFs and microwaves. Additionally, current and future perspectives of the topic have been discussed.

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Amidation, Esterification, and Thioesterification of a Carboxyl‐Functionalized Covalent Organic Framework

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.

Cited by 30 publications

References 32 publications

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

Anhydride Post-Synthetic Modification in a Hierarchical Metal–Organic Framework

Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis

Microwave‐Assisted Synthesis of Covalent Organic Frameworks: A Review

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