Olefin metathesis reaction as a locking tool for macrocycle and mechanomolecule construction

Quaglio, Deborah; Zappia, Giovanni; Paolis, Elisa De; Balducci, Silvia; Botta, Bruno; Ghirga, Francesca

doi:10.1039/c8qo00728d

Cited by 30 publications

(20 citation statements)

References 124 publications

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“…Where bonds are not formed reversibly, the formation of off-pathway kinetic products can limit the yield of a desired species, rendering product isolation challenging. Higher yields and cleaner products may be obtained through the use of templates 8 and reversibly formed linkages 9 such as imines, 10 boronic esters, 11 and alkenes 12 or alkynes 13 (with appropriate catalysts). The use of such dynamic covalent bonds leads to the formation of thermodynamic products, but such products may show limited stability due to cleavage of the dynamic bonds, such as hydrolysis of imines.…”

Section: Introductionmentioning

confidence: 99%

Metal and Organic Templates Together Control the Size of Covalent Macrocycles and Cages

2019

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Covalent macrocycles and three-dimensional cages were prepared by the self-assembly of di- or tritopic anilines and 2,6-diformylpyridine subcomponents around palladium(II) templates. The resulting 2,6-bis(imino)pyridyl-PdII motif contains a tridentate ligand, leaving a free coordination site on the PdII centers, which points inward. The binding of ligands to the free coordination sites in these assemblies was found to alter the product stability, and multitopic ligands could be used to control product size. Multitopic ligands also bridged metallomacrocycles to form higher-order supramolecular assemblies, which were characterized via NMR spectroscopy, mass spectrometry, and X-ray crystallography. An efficient method was developed to reduce the imine bonds to secondary amines, leading to fully organic covalent macrocycles and cages that were inaccessible through other means.

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Section: Introductionmentioning

confidence: 99%

Metal and Organic Templates Together Control the Size of Covalent Macrocycles and Cages

2019

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“…Having established an efficient and scalable strategy toward the thiol precursors of these macrocycles, we then optimized our reaction conditions for the macrocyclization (Table ). The first macrocycle ( 3 ca ) was obtained in 68 % yield using this ring‐closing sulfur‐bond metathesis strategy . Interestingly, using our previous catalytic system (Pd‐SingaCycle A1), even with a higher catalyst loading of 10 %, the same macrocycle was formed in less than 20 % yield.…”

Section: Methodsmentioning

confidence: 94%

Nickel‐Catalyzed Inter‐ and Intramolecular Aryl Thioether Metathesis by Reversible Arylation

et al. 2019

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An ickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers.1 ,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore,s ynthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds.In-depth organometallic studies support ar eversible Ni 0 /Ni II pathway to product formation. Overall, this work not only provides am ore sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.Aryl thioethers are often found in natural products, [1] Scheme 1. Context of the work.

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“…This reaction, in combination with chiral catalysts, has been reported in the total synthesis of complex alkaloids [ 59 ]. Another synthetic approach widely employed for the construction of sophisticated macromolecules architecture, such as alkaloids, is the olefin metathesis reaction, which is one of the most powerful tools for the formation of challenge polycyclic frameworks and bridged nitrogen heterocycles [ 60 , 61 , 62 ]. Most of the alkaloids reported below are known and their multiple chiral centers were assigned according to the literature.…”

Section: Alkaloidsmentioning

confidence: 99%

Naturally-Occurring Alkaloids of Plant Origin as Potential Antimicrobials against Antibiotic-Resistant Infections

et al. 2020

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Antibiotic resistance is now considered a worldwide problem that puts public health at risk. The onset of bacterial strains resistant to conventional antibiotics and the scarcity of new drugs have prompted scientific research to re-evaluate natural products as molecules with high biological and chemical potential. A class of natural compounds of significant importance is represented by alkaloids derived from higher plants. In this review, we have collected data obtained from various research groups on the antimicrobial activities of these alkaloids against conventional antibiotic-resistant strains. In addition, the structure–function relationship was described and commented on, highlighting the high potential of alkaloids as antimicrobials.

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Olefin metathesis reaction as a locking tool for macrocycle and mechanomolecule construction

Abstract: The present review deals with an updated visit to the olefin metathesis reaction as a powerful tool for the construction of sophisticated macromolecular architectures.

Cited by 30 publications

References 124 publications

Metal and Organic Templates Together Control the Size of Covalent Macrocycles and Cages

Metal and Organic Templates Together Control the Size of Covalent Macrocycles and Cages

Nickel‐Catalyzed Inter‐ and Intramolecular Aryl Thioether Metathesis by Reversible Arylation

Naturally-Occurring Alkaloids of Plant Origin as Potential Antimicrobials against Antibiotic-Resistant Infections

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