We report an efficient method for the regiodivergent synthesis of halogenated resorcinol derivatives using readily available vinylogous esters and sulfonyl halide halogen donors. Either the 4- or 6-haloresorcinol isomer is accessible from a common precursor. In contrast to conventional oxidants for arene halogenation, mild sulfonyl halides allow broad functional group compatibility. The strategy inherently differentiates the two resorcinol oxygen atoms and enhances the potential for complex molecule synthesis.
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http://dx.doi.org/10.1021/ol503561x | DOI Listing |
Chem Asian J
January 2025
Indian Institute of Science Education and Research Thiruvananthapuram, chemistry, 2204, School of Chemistry, Vithura, 695551, Thiruvananthapuram, INDIA.
A one-pot methodology for the tandem acylation and oxidative aromatization of vinylogous thioesters to 2-acyl-5-(alkyl/arylthio)phenols is presented. Initially, cyclohexane-1,3-diones were converted to vinylogous thioesters through FeCl3-mediated thioenolization. This was followed by LiTMP-mediated acylation and DDQ-mediated aromatization, which resulted in the synthesis of sulphur derived oxybenzone analogs.
View Article and Find Full Text PDFNat Commun
December 2024
Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, China.
The functionalized polycycle with densely contiguous tertiary stereocenters is a formidable challenge in synthesizing the parvistemoline family of Stemona alkaloids. We herein report their catalytic, asymmetric total syntheses in 13-14 steps from commercially available 2-(methoxycarbonyl)-pyrrole, featuring the development and deployment of an Ir/Pd-synergistically-catalyzed allylation of α-non-substituted keto esters with secondary aryl-substituted alcohols, stereodivergently accessible to four stereoisomers. Using chiral Pd-enolate and Ir π-allyl complex under neutral conditions, no epimerization occurs.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Applied Chemistry, National Yang Ming Chiao Tung University, 1001 University Road, Hsinchu 30010, Taiwan.
This study presents a method for synthesizing functionalized hydrodibenzofuran derivatives. Using palladium catalysis, -aryl cyclic vinylogous esters undergo dehydrogenative intramolecular arylation at the vinylic carbon. Preliminary kinetic isotope effect studies suggest that the C(aryl)-H bond cleavage may be the rate-determining step.
View Article and Find Full Text PDFEJNMMI Radiopharm Chem
November 2024
School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, University of Melbourne, Parkville, VIC, 3010, Australia.
Background: Carbonic Anhydrase IX (CAIX) is a zinc metalloenzyme that is over-expressed in many cancers making it a valid target for targeted diagnostic imaging with Positron Emission Tomography (PET). The monoclonal antibody girentuximab binds to CAIX and when radiolabelled with positron-emitting zirconium-89 can be used for diagnostic PET imaging of CAIX positive tumours.
Results: Reaction of desferrioxamine squaramide ethyl ester with girentuximab allowed isolation of a conjugate with desferrioxamine squaramide (DFOSq) covalently attached to girentuximab through stable vinylogous amide linkages to give DFOSq-girentuximab.
J Org Chem
November 2024
School of Chemistry, Indian Institute of Science Education and Research, Thiruvananthapuram, Kerala 695551, India.
This study demonstrates the direct conversion of vinylogous esters into selectively protected 6-acyl resorcinols (4-alkoxy/aryloxy-2-hydroxy arylketones) in a regiospecific manner. Resorcinyl ketones are first-time synthesized, diverging from their traditional roots, originating from non-benzenoid pool materials. Converting cyclohexenones into phenol- or resorcinol-based arylketones remains challenging due to the stability and reactivity issues of intermediate products.
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