We report an unprecedented highly enantioselective desymmetric Cu(I)-catalyzed 1,3-dipolar cycloaddition of diazides with terminal alkynes and 1-iodoalkynes, affording tertiary alcohols bearing a 1,2,3-triazole moiety in high yield and excellent ee value. PYBOX ligands with a C4 shielding group once again show the promising ability to achieve higher enantioselectivity.
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http://dx.doi.org/10.1021/acs.orglett.9b04522 | DOI Listing |
Chem Asian J
November 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER), Jatni, Bhubaneswar, Odisha, 752050, India.
Synthesizing molecules with significant topological features, such as catenanes, tailored with specific groups to confer desired functionality, is essential for investigating various properties arising from the entanglement due to mechanical bonds. This investigation can pave the way for uncovering novel functional materials employing mechanically interlocked molecules (MIMs). In this direction, we have synthesized a π-donor (D) and π-acceptor (A) functionalized [2]catenane using a non-labile Co(III) metal ion as a template with pyridine-diamide templating center and utilizing click reaction for ring-closing.
View Article and Find Full Text PDFOrg Lett
May 2024
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710127, P.R. China.
The synthesis of complex alkanes by the tetrafunctionalization of alkynes is limited and challenging. Herein, an unprecedented efficient geminal diazidation and dibromination of terminal alkynes is developed, which provides novel access to structurally diverse organic azides. The approach has exclusive chemo- and regioselectivity and features mild reaction conditions, good tolerance of various functional groups, and more crucially, no metal involved in the reaction, thereby benefiting the late-stage decoration of medicinal molecules.
View Article and Find Full Text PDFMacromol Rapid Commun
May 2024
Université Claude Bernard Lyon 1, CNRS, Ingénierie des Matériaux Polymères, UMR 5223, Lyon, F-69003, France.
A tetra(ethylene glycol)-based 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) is synthesized in two steps including: i) the catalyst-free polyaddition of a diazide and an activated internal dialkyne and ii) the N-alkylation of the resulting 1,2,3-triazole groups. In order to provide detailed structure/properties correlations different analogs are also synthesized. First, parent poly(1,2,3-triazole)s are obtained via AA+BB polyaddition using copper(I)-catalyzed alkyne-azide cycloaddition or metal-free thermal alkyne-azide cycloaddition (TAAC).
View Article and Find Full Text PDFChem Sci
December 2023
Department of Chemistry, Rice University 6100 Main St MS 602 Houston TX 77005 USA
Ligand-to-metal charge transfer (LMCT) is a mechanistic strategy that provides a powerful tool to access diverse open-shell species using earth abundant elements and has seen tremendous growth in recent years. However, among many reaction manifolds driven by LMCT reactivity, a general and catalytic protocol for modular difunctionalization of alkenes remains unknown. Leveraging the synergistic cooperation of iron-catalyzed ligand-to-metal charge transfer and radical ligand transfer (RLT), here we report a photocatalytic, modular difunctionalization of alkenes using inexpensive iron salts catalytically to function as both radical initiator and terminator.
View Article and Find Full Text PDFJ Control Release
April 2023
NMPA Key Laboratory for Research and Evaluation of Drug Metabolism & Guangdong Provincial Key Laboratory of New Drug Screening, School of Pharmaceutical Sciences, Southern Medical University, Guangzhou 510515, PR China; Department of Ultrasonic Diagnosis, Zhujiang Hospital, Southern Medical University, Guangzhou 510282, PR China. Electronic address:
Polyprodrug nanomedicines hold great potential for combating tumors. However, the functionalization of polyprodrug nanomedicines to improve therapeutic efficacy is restricted by conventional polymerization methods. Herein, we fabricated a charge-conversional click polyprodrug nanomedicine system by metal-free azide-alkyne cycloaddition click polymerization (AACCP) for targeted and synergistic cancer therapy.
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