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A facile, transition metal-free method has been developed for the synthesis of thiocyano-thioesters. It employs cyclic thioacetals and aryl thiocyanate as an organic 'CN' source, facilitated by organophotocatalyst under the visible light irradiation. Additionally, the diaryl disulfide by-products have been efficiently repurposed as a recyclable and reusable substrates for the sustainable synthesis of aryl thiocyanates, supporting the circular chemical economy. This method exhibits broad functional group tolerance and is applicable to five- to eight-membered cyclic thioacetals. The method also proved to be scalable on gram quantity. A series of control experiments, fluorescence quenching, and cyclic voltammetry analysis supported the proposed reaction mechanism.
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http://dx.doi.org/10.1002/asia.202500423 | DOI Listing |
Chem Asian J
June 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhabha Road, NCL Colony, Pashan, Pune, Maharashtra, 411008, India.
A facile, transition metal-free method has been developed for the synthesis of thiocyano-thioesters. It employs cyclic thioacetals and aryl thiocyanate as an organic 'CN' source, facilitated by organophotocatalyst under the visible light irradiation. Additionally, the diaryl disulfide by-products have been efficiently repurposed as a recyclable and reusable substrates for the sustainable synthesis of aryl thiocyanates, supporting the circular chemical economy.
View Article and Find Full Text PDFChemistry
September 2024
Department of Chemistry, University College London, 20, Gordon Street, London, WC1H 0AJ, UK.
Cyclisation of peptides by forming thioether (lanthionine), disulfide (cystine) or methylene thioacetal bridges between side chains is established as an important tool to stabilise a given structure, enhance metabolic stability and optimise both potency and selectivity. However, a systematic comparative study of the effects of differing bridging modalities on peptide conformation has not previously been carried out. In this paper, we have used the NMR deconvolution algorithm, NAMFIS, to determine the conformational ensembles, in aqueous solution, of three cyclic analogues of angiotensin(1-7), incorporating either disulfide, or non-reducible thioether or methylene thioacetal bridges.
View Article and Find Full Text PDFJACS Au
September 2023
Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland.
Progress with fluorescent flippers, small-molecule probes to image membrane tension in living systems, has been limited by the effort needed to synthesize the twisted push-pull mechanophore. Here, we move to a higher oxidation level to introduce a new design paradigm that allows the screening of flipper probes rapidly, at best . Late-stage clicking of thioacetals and acetals allows simultaneous attachment of targeting units and interfacers and exploration of the critical chalcogen-bonding donor at the same time.
View Article and Find Full Text PDFActa Biomater
August 2023
School of Biomedical Sciences and Engineering, South China University of Technology, Guangzhou International Campus, Guangzhou 511442, PR China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou 510006, PR China. Electroni
Tumor-associated enzyme activated prodrug is a potential strategy to overcome the limitations of chemotherapeutic agents. However, the efficiency of enzymatic prodrug activation is limited by the inability to reach adequate enzyme levels in vivo. Herein, we report an intelligent nanoplatform with cyclic amplification of intracellular reactive oxygen species (ROS) that significantly up-regulates the expression of tumor-associated enzyme, NAD(P)H:quinone oxidoreductase 1 (NQO1), to efficiently activate the prodrug of doxorubicin (DOX) for enhanced chemo-immunotherapy.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2023
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan.
We report a novel method to synthesize degradable poly(vinyl ether)s with cleavable thioacetal bonds periodically arranged in the main chains using controlled cationic copolymerization of vinyl ethers with a 7-membered cyclic thioacetal (7-CTA) via degenerative chain transfer (DT) to the internal thioacetal bonds. The thioacetal bonds, which are introduced into the main chain by cationic ring-opening copolymerization of 7-CTA with vinyl ethers, serve as in-chain dormant species to allow homogeneous propagation of vinyl ethers for all internal segments to afford copolymers with controlled overall and segmental molecular weights. The obtained polymers can be degraded into low- and controlled-molecular-weight polymers with narrow molecular weight distributions via hydrolysis.
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