Phosphine-catalyzed [2 + 4] annulation of allenoates with thiazolone-derived alkenes has been achieved under mild conditions, giving biologically important 6,7-dihydro-5H-pyrano[2,3-d]thiazole derivatives in high to excellent yields. With the use of Kwon's phosphine as the chiral catalyst, optically active products were obtained in good yields with excellent enantioselectivities.
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http://dx.doi.org/10.1021/acs.orglett.6b01571 | DOI Listing |
Org Lett
January 2025
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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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.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry, China Agricultural University, 2 West Yuanmingyuan Road, Beijing, 100193, P. R. China.
Chiral 2-azetines and allenes are highly valuable structural units in natural products and useful chemicals. However, enantioselective synthesis of both 2-azetines and allenes has been extremely challenging. Herein, we present asymmetric construction of chiral 2-azetines (70-98 % yields and up to 96 % ee) through chiral phosphine-catalyzed [2+2] annulation of yne-enones with sulfamate-derived cyclic imines.
View Article and Find Full Text PDFJ Org Chem
November 2024
College of Chemistry, Tianjin Normal University, Tianjin 300387, China.
A phosphine-catalyzed [4 + 1] annulation of β'-acetoxy allenoate with α-alkylidene succinimides is described. This method demonstrates the nucleophilic dialkylation and cyclization of α-alkylidene succinimides, resulting in the formation of functionalized spirosuccinimide derivatives. The reaction exhibits a wide substrate scope and yields ranging from moderate to excellent under the optimized conditions.
View Article and Find Full Text PDFOrg Lett
November 2024
State Key Laboratory of Natural Medicines, Department of Organic Chemistry, China Pharmaceutical University, Nanjing 210009, P. R. China.
Herein we reported a novel strategy for constructing benzoxepine fused succinimide derivatives via a phosphine-catalyzed [3 + 4] cyclization of α-substituted allenes and salicylaldehyde Schiff bases. This methodology serves as a conduit for the construction of benzoxepine derivatives in good yields under mild conditions by an unprecedented mode involving the β'-carbon of allenes. Density functional theory calculations were conducted to study the possible mechanism.
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