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A Cu(I)-catalyzed [4 + 1] cycloaddition reaction between -quinone methides and terminal alkynes has been developed, demonstrating good compatibility with both stable and in situ generated -quinone methides. This methodology offers several significant advantages, including operational simplicity, wide substrate compatibility, and the ability to access synthetically useful 2,3-disubstituted benzofuran compounds in generally good to high yields (44 examples, up to 91% yield).
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http://dx.doi.org/10.1021/acs.joc.5c00624 | DOI Listing |
Org Lett
September 2025
School of Chemistry and Chemical Engineering, Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development, Guangxi University, Nanning 530004, China.
Vinylphosphonates serve as crucial components in synthetic chemistry, medicinal chemistry, and materials science. However, traditional synthetic methods for these compounds typically require the use of noble metal catalysts and hazardous reagents. Herein, we report a metal-free strategy for the divergent synthesis of vinylphosphonates through the P nucleophilic addition of vinylidene -quinone methides (-VQMs).
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September 2025
Department of Chemistry, Sungkyunkwan University, Jangan, Suwon, 16419, Korea.
We report an efficient Lewis acid catalyzed enantioselective synthesis of diarylindolylmethanes via in situ generated -quinone methides. The protocol enables selective Friedel-Crafts alkylation at indole C3, and by blocking this site, extends selectively to C2 position. Mechanistic studies, including quantum calculations and Hammett analysis, reveal selectivity arising from β-methide steric hindrance and catalyst-substrate π-π interactions.
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August 2025
Faculty of Pharmacy and Pharmaceutical Sciences, Josai University 1-1 Keyakidai, Sakado Saitama 350-0295 Japan
Among various treatment options for diabetes, insulin therapy remains an important approach, but it inevitably carries the risk of hypoglycaemia, particularly due to dosing errors or unexpected glucose fluctuations. To address this challenge, glucose-responsive insulin delivery systems that release insulin based on blood glucose levels have emerged as a promising solution. In this study, we developed a fully dissolved glucose-responsive insulin delivery system using -borono-phenylmethoxycarbonyl-modified insulin aspart (BPmoc-Ins-Asp) and glucose oxidase (GOx).
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September 2025
Department of Chemistry, University of Delhi, Delhi 110007, India.
Herein, we demonstrate a [2+2] cycloaddition/electrocyclic ring-opening reaction between quinone methide and electronically unbiased terminal alkynes under strictly thermal conditions. The present investigation is a unique example that demonstrates the effect of extended conjugation and cross-conjugation on the energy of the lowest unoccupied molecular orbital. As supported by density functional theory calculations, the reaction proceeds through the biradical pathway, accommodating both electron-deficient and electron-rich alkyne partners.
View Article and Find Full Text PDFMol Divers
August 2025
School of Pharmacy and Food Engineering, Wuyi University, Jiangmen, 529020, Guangdong, China.
We report a visible-light-driven asymmetric three-component reaction enabling direct enantioselective C2-functionalization of indoles. This method utilizes arylalkynes, benzoquinones, and indoles under chiral phosphoric acid catalysis to construct chiral indole derivatives bearing all-carbon quaternary stereocenters. The reaction proceeds via a cascade sequence: (1) Paternò-Büchi [2 + 2] cycloaddition between arylalkynes and benzoquinones, (2) electrocyclic ring-opening to generate para-quinone methide intermediates, and (3) enantioselective 1,6-addition of indoles at C2 to the para-quinone methide.
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