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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). This method provides a variety of 1,2-diaryl vinylphosphates in good yields (up to 85% yield), which represents a unique example of -VQMs for C-P bond formation. The protocol features mild reaction conditions, a green solvent, broad functional group compatibility, and environmental friendliness.
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http://dx.doi.org/10.1021/acs.orglett.5c03542 | 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).
View Article and Find Full Text PDFOrg Lett
April 2025
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, China.
Herein, for the first time, the controllable, accurate, and diverse synthesis of all ring sizes of medium-sized (8- to 11-membered) indole-derived bridged biaryls has been realized by using ingeniously designed -alkynylnaphthols that feature cyclic amines with adjustable ring sizes. The transformation may proceed through a DBN-mediated in-situ generation of vinylidene -quinone methides/indole-ring formation/ring expansion cascade sequence, which is characterized by acceptable to excellent yields and good functional group tolerance.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Axially chiral -VQMs have been extensively investigated as key intermediates to approach miscellaneous chiral structures. By sharp contrast, their structural isomers -VQMs have not been previously documented. The major reason, which results in the significant delay, may ascribe to the inherent challenges in the enantioselective activation of alkynes in a remote manner.
View Article and Find Full Text PDFNat Commun
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing, China.
Helicene-shaped molecules are compelling chemical structures with unique twisted helical chirality and remarkable properties. Although progress occurs in the catalytic asymmetric synthesis of helicene (-like) molecules, the enantioselective synthesis of multiple helicenes, especially four or higher helicity, is still challenging and has yet to be achieved. Herein, we report an organocatalytic [4 + 2] cycloadditions to achieve double S-shaped quadruple helicene-like molecules with high enantioselectivity (up to 96% e.
View Article and Find Full Text PDFMacromol Rapid Commun
March 2025
Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa, 56124, Italy.
This study presents the preparation and electrochemical testing of sulfonated styrene-grafted poly(vinylidene fluoride) (pVDF) copolymers as proton exchange membranes (PEMs) for semi-organic redox flow batteries (RFBs) based on 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/bromine. The copolymers are synthesized via a two-step procedure, involving i) atom transfer radical polymerization of styrene (Sty) for the grafting to the pVDF backbone and ii) the sulfonation of the polystyrene grafted side chains. Copolymers with different amounts of sulfonated styrene (SSty) in the side chains (i.
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