A General Method for High-Pressure-Promoted Postfunctionalization of Unclosed Cryptands: Potential Phase-Transfer Catalysts

Tyszka-Gumkowska, Agata; Jurczak, Janusz

doi:10.1021/acs.joc.9b02985

Cited by 6 publications

(3 citation statements)

References 42 publications

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“…The lariat arm, apart from bringing extra hydrogen bond functionality, introduces a steric hindrance to the binding cavity and further pre-organizes the macrocyclic framework [41][42][43][44]. To date, this robust macrocyclic platform has been utilized for the construction of potent and selective anion receptors [41,[45][46][47][48][49], phase transfer catalysts (PTC) [50,51], and closely packed molecular hosts for solid-state stabilization of transient supramolecular assemblies such as water clusters [52][53][54] and S• • • S chalcogen bonds [55]. Recently, we have developed practical and productive methods for the synthesis of these systems, using templated-macrocyclization protocols [48,55,56] and post-macrocyclization incorporation of lariat arms under mild conditions [43,46,47,56,57].…”

Section: Introductionmentioning

confidence: 99%

Anion Recognition by a Pincer-Type Host Constructed from Two Polyamide Macrocyclic Frameworks Jointed by a Photo-Addressable Azobenzene Switch

et al. 2022

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A sterically crowded light-responsive host 1 was synthetized with a 93% yield by applying a post-functionalization protocol utilizing the double amidation of 4,4′-azodibenzoyl dichloride with a readily available 26-membered macrocyclic amine. X-ray structures of two hydrates of trans-1 demonstrate a very different alignment of the azobenzene linkage, which is involved in T-shape or parallel-displaced π⋯π stacking interactions with the pyridine-2,6-dicarboxamide moieties from the macrocyclic backbone. Despite the rigidity of the macrocyclic framework, which generates a large steric hindrance around the azobenzene chromophore, the host 1 retains the ability to undergo a reversible cis⟷trans isomerization upon irradiation with UVA (368 nm) and blue (410 nm) light. Moreover, thermal cis→trans back-isomerization (ΔG0 = 106.5 kJ∙mol−1, t½ = 141 h) is markedly slowed down as compared to the non-macrocyclic analog. 1H NMR titration experiments in DMSO-d6/0.5% water solution reveal that trans-1 exhibits a strong preference for dihydrogenphosphate (H2PO4−) over other anions (Cl−, MeCO2−, and PhCO2−), whereas the photogenerated metastable cis-1 shows lower affinity for the H2PO4− anion.

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Section: Introductionmentioning

confidence: 99%

Anion Recognition by a Pincer-Type Host Constructed from Two Polyamide Macrocyclic Frameworks Jointed by a Photo-Addressable Azobenzene Switch

et al. 2022

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“…Unclosed cryptands (UCs) [22][23][24][25][26][27] belong to the class of fairly new macrocyclic receptors, structurally related to well-established cryptands [28][29][30][31][32]. They are, however, much more flexible than their rigid analogs, as they are built from the macroring of various sizes to which is connected a labile intrannular substituent-lariat arm.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of Near Identical Hydrogen Bonded Octameric Water Clusters in Crystal Structures of Three Distinct Non-Charged Polyamide Macrocyclic Host Molecules

2021

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In this paper, we present a comparative analysis of the solid state structures of three well-resolved hydrates of macrocyclic host molecules 1a, 1b, and 2 containing an intrannular amide-aryl substituent (lariat arm) connected to a fixed 26-membered ring in a normal (-NHCOAr, hosts 1a and 1b) or reverse manner (-CONHAr, host 2). Despite different chemical structures, these hosts crystallize as isostructural tetrahydrates in the same P-1 space group. Moreover, their crystals exhibit identical hydrogen bond motifs resulting in a stabilization of an almost identical unusual octameric water cluster built from the cyclic tetramer core and four water molecules, attached sequentially in an “up-and-down” manner. Further analysis reveals that, among the series, the structure of host 2 provides the most suitable environment for the accommodation of this type of water cluster.

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“…Searching for efficient pathways to obtain macrocyclic compounds, which can find applications in supramolecular chemistry as molecular receptors, , sensors, − and catalysts, − is one of the main topics of our long-term research. We previously developed two synthetic procedures addressing this problem: macrocyclization under high-pressure conditions via double quaternization of diamines by α,ω-diiodide compounds − and via double amidation of dimethyl esters by α,ω-diamines…”

Section: Introductionmentioning

confidence: 99%

Static Combinatorial Chemistry: A High-Pressure Approach to the Synthesis of Macrocyclic Benzoamide Libraries

2020

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We investigated the yield and distribution of macrocyclic products formed in combinatorial libraries (CLs) obtained via double-amidation reactions of methyl diesters with α,ω-diamines. The application of the static combinatorial chemistry (SCC) approach allowed us to generate a large number of macrocyclic diamides and tetraamides in single experiments. We show that high-pressure conditions accelerate the macrocyclization process but also have a great impact on the distribution of macrocyclic products in the presented libraries, promoting the formation of macrocyclic compounds and eliminating the linear ones. The distribution of macrocyclic products was also found to be strongly dependent on the structural features of the substrates employed. Furthermore, in three- and four-substrate CLs we observed the formation of a new type of hybrid tetraamides consisting of three different components.

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A General Method for High-Pressure-Promoted Postfunctionalization of Unclosed Cryptands: Potential Phase-Transfer Catalysts

Cited by 6 publications

References 42 publications

Anion Recognition by a Pincer-Type Host Constructed from Two Polyamide Macrocyclic Frameworks Jointed by a Photo-Addressable Azobenzene Switch

Anion Recognition by a Pincer-Type Host Constructed from Two Polyamide Macrocyclic Frameworks Jointed by a Photo-Addressable Azobenzene Switch

Stabilization of Near Identical Hydrogen Bonded Octameric Water Clusters in Crystal Structures of Three Distinct Non-Charged Polyamide Macrocyclic Host Molecules

Static Combinatorial Chemistry: A High-Pressure Approach to the Synthesis of Macrocyclic Benzoamide Libraries

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