Copper-Mediated Deconstructive Ring Cleavage of Cyclic Thioethers with Boron Compounds

Wang, Guanyu; Han, Do Soon; Li, Yue; Nie, Yangleiyu; Muthusamy, Selvaraj; Luo, Zhibin; Liu, Bin

doi:10.1021/acs.orglett.3c01100

Cited by 6 publications

(4 citation statements)

References 52 publications

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“…We previously reported a copper-mediated Chan−Lam type coupling of boronic acids and thioethers to give sulfonium salts. 13 By introducing thioureas as the sulfur source, arylisothiouronium salts were successfully generated in the same fashion, as shown in Scheme 3, B.…”

Section: Resultsmentioning

confidence: 99%

The Chan-Lam-type synthesis of thioimidazolium salts for thiol-(hetero)arene conjugation

Li,

Han,

Luo

et al. 2024

Preprint

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The design of stable and variable aryl linkers for conjugating drug moieties to the metabolism-related thiols is of importance in drug discovery, especially in the field of antibody-drug conjugates (ADCs). We disclosed that thioimidazolium groups are unique scaffolds for the thiol-(hetero)arene conjugation under mild conditions. The drug bound thioimidazolium salts, which are easily accessible via a copper-mediated Chan-Lam process in gram-scale, could be successfully applied to the late-stage coupling of bioactive thiols to construct a broad array of drug-like molecules.

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Section: Resultsmentioning

confidence: 99%

The Chan-Lam-type synthesis of thioimidazolium salts for thiol-(hetero)arene conjugation

Li,

Han,

Luo

et al. 2024

Preprint

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“…In fact, most of the arylboronic acids are highly emissive in dilute states, and weak multiple color afterglow could also be observed at low temperatures. , They usually contain heteroatoms, carbonyl, and phenyl groups, which are favorable for increasing the ISC efficiency. In addition, the vacant p orbitals of B atoms are reported to be effective functional sites to interact with π–π* and n–π* transitions, which could be used as the luminescence center to modulate and expand the afterglow colors. , This demonstrates the great possibility of increasing the afterglow intensity of arylboronic acids and further tuning their color by utilizing proper strategies such as host–guest doping. For example, Zhang and co-workers doped 9-phenylcarbazol-2-ylboronic acid into poly(vinyl alcohol) (PVA) matrices, and the afterglow lifetime and emission color were tuned by controlling the chemical and physical reactions between host and guest molecules .…”

Section: Introductionmentioning

confidence: 99%

Wide-Color-Tunable Afterglow Materials from Blue to Deep Red via Boric Acid Assisted Molecular Doping

Chen,

Fu,

Chang

et al. 2024

J. Phys. Chem. C

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The construction of afterglow materials with full-color tunable emissions is attractive but still a challenging task. Herein, a host–guest doping strategy was proposed to produce afterglow materials with an emission-color span of almost 210 nm (from blue to deep red) by heat treating the aqueous mixture of arylboronic acids and boric acid (BA). In-depth structural, photophysical, and theoretical studies revealed that the heat treatment process resulted in the dehydration of BA and the formation of a glassy state host, and arylboronic acids were loaded as guest molecules through H-bonds and covalent bonds with BA. The afterglow originated from arylboronic acids, and the afterglow color of products was related to their degree of conjugation of aromatic groups. The host–guest doping strategy significantly improved the photophysical performances of arylboronic acids, achieving a photoluminescence quantum yield as high as 81.7% and an emission lifetime of 2.90 s (afterglow >22 s). Triple information encryption based on emission lifetime and color-encoding was also achieved, demonstrating their commercial potential for use in anticounterfeiting and information storage.

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“…Sulfoxides bearing a unique sulfinyl group are very important functional groups that have found applications in various fields, including asymmetric organic synthesis, functional materials, and medicinal chemistry. , An example of a pharmaceutical containing a sulfoxide moiety is esomeprazole, a proton pump inhibitor used against acid-related diseases . Generally, sulfoxides can be prepared by selectively oxidizing thioethers, which can be readily accessed through transition-metal-catalyzed Chan-Lam cross-coupling. − In 2015, Hosoya and co-workers reported an efficient synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates under mild conditions …”

Section: Introductionmentioning

confidence: 99%

Copper(II) Surface-Functionalized Porous Organic Polymers for One-Pot Synthesis of Sulfoxide via Chan-Lam Cross-Coupling and Photooxidation Reactions

Lin,

Zheng,

et al. 2024

ACS Appl. Polym. Mater.

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Nanometer-sized porous organic polymers (POPs) composed of 4,4difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) and tetraphenylmethane units were synthesized via Sonogashira coupling reactions under mini-emulsion conditions. Furthermore, a post-synthetic strategy was employed to covalently attach copper(II)−phenanthroline complexes to the surface of the POP nanoparticles through a thiol-yne click reaction. Detailed characterization of the photocatalyst, TEPM−BDP−Phen@Cu, using techniques such as solid-state nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, energy-dispersive spectroscopy, and inductively coupled plasma atomic emission spectrometry demonstrated that the copper(II)− phenanthroline complexes were successfully anchored on the surface of the POPs. TEPM−BDP−Phen@Cu exhibited dual catalytic activities, enabling it to catalyze the Chan-Lam cross-coupling reaction by external copper complexes and photocatalytically oxidize thioanisole into the corresponding sulfoxide by internal BODIPY-based polymeric networks via singlet oxygen. Taking the synthesis of methyl phenyl sulfoxide as the model reaction, TEPM−BDP−Phen@Cu was proven to be a good heterogeneous catalyst for the one-pot synthesis of methyl phenyl sulfoxide from S-methyl 4-toluenethiosulfonate and phenylboronic acid with a yield of 78%. Importantly, this reaction could be performed under mild conditions (room temperature, atmospheric pressure, and oxygen molecules in air as the oxidant) and avoid unpleasant odors of thioethers.

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Copper-Mediated Deconstructive Ring Cleavage of Cyclic Thioethers with Boron Compounds

Cited by 6 publications

References 52 publications

The Chan-Lam-type synthesis of thioimidazolium salts for thiol-(hetero)arene conjugation

The Chan-Lam-type synthesis of thioimidazolium salts for thiol-(hetero)arene conjugation

Wide-Color-Tunable Afterglow Materials from Blue to Deep Red via Boric Acid Assisted Molecular Doping

Copper(II) Surface-Functionalized Porous Organic Polymers for One-Pot Synthesis of Sulfoxide via Chan-Lam Cross-Coupling and Photooxidation Reactions

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