An enantio-, diastereo-, regio-, and chemoselective phosphine-catalyzed β,γ-umpolung domino reaction of allenic esters with dienones has been developed for the first time. The designed sequence, involving oxy-Michael and Rauhut-Currier reactions, produced highly functionalized tetrahydrobenzofuranones, bearing a chiral tetrasubstituted stereogenic center, in up to 96 % ee.
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Phosphine-Catalyzed Cascade Cycloaddition of Vinyl Oxiranes with Sulfonium Compounds to Step-Economically Construct Spiro-2(3)-furanone Scaffolds.
Org Lett
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School of Pharmaceutical Sciences and Institute of Materia Medica, Medical Science and Technology Innovation Center, Shandong First Medical University and Shandong Academy of Medical Sciences, Jinan, Shandong 250117, P. R. China.
In this work, we developed a phosphine-catalyzed cascade lactonization/[2 + 1] annulation reaction between vinyl oxiranes and sulfonium compounds for the highly diastereoselective construction of spiro-2(3)-furanone skeletons. The cascade cycloaddition proceeds via the 2(5)-furanone phosphonium intermediate, introducing an oxygen-containing active intermediate for phosphine catalysis. These findings highlight the significant potential of harnessing vinyl oxiranes as versatile synthons for constructing spirocyclic compounds through simultaneous multicyclic skeleton formation.
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Org Lett
December 2024
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei 443002, China.
An unexpected phosphine-catalyzed controllable three-component domino reaction involving [1 + 2 + 2] annulation and [1 + 2 + 2]/[3 + 2] sequential annulation reaction of 2-arylmethylidene cyanoacetates/malononitriles with Morita-Baylis-Hillman (MBH) carbonates has been developed. A broad range of densely functionalized cyclopentanes and diquinanes bearing five or four consecutive stereogenic centers, including two all-carbon quaternary stereocenters, were smoothly acquired in moderate to excellent yields under mild reaction conditions from readily available materials. Moreover, this divergent transformation enables the simultaneous generation of three or four new C-C bonds and one or two carbocyclic rings in only one step.
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Org Biomol Chem
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Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, 136 Science Avenue, 450001, Zhengzhou, Henan Province, P.R. China.
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Angew Chem Int Ed Engl
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Department of Chemistry, China Agricultural University, 2 West Yuanmingyuan Road, Beijing, 100193, P. R. China.
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College of Chemistry, Tianjin Normal University, Tianjin 300387, China.
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