The Zn(II)/UCD-Imphanol-catalyzed highly -selective [3 + 2] asymmetric cycloaddition of acyclic enones and azomethine ylides has been developed. Moderate to high yields (up to 94%) with excellent / selectivities (99 : 1) and enantioselectivities up to 96.5 : 3.5 er were obtained.
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http://dx.doi.org/10.1039/d4ob00854e | DOI Listing |
Org Lett
January 2025
State Key Laboratory of Southwestern Chinese Medicine Resources, School of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 611137, P. R. China.
Herein, we introduce a scandium-catalyzed synthetic strategy that provides access to a diverse and functionalized array of cyclobutene frameworks adorned with a quaternary carbon center. This approach broadens the synthetic repertoire of 2-alkynylnaphthols with alkenes, offering a versatile platform for the construction of complex molecular architectures. The asymmetric catalytic [2 + 2] cycloaddition reaction demonstrates a wide substrate scope and an impressive functional group tolerance, yielding products with high efficiency, up to 97% yield, and excellent enantiomeric excess of up to 97%.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shandong University, Department of Chemistry, 27 South Shanda Road, 250100, Jinan, CHINA.
Planar chirality found tremendous use in many fields, such as chemistry, optics, and materials science. In particular, planar chiral [2.2]paracyclophanes (PCPs) are a type of structurally interesting and practically useful chiral compounds bearing unique electronic and photophysical properties and thus have been widely used in π-stacking polymers, organic luminescent materials, and as a valuable toolbox for developing chiral ligands or organocatalysts.
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 PDFOrg Lett
January 2025
Department of Chemistry, Indian Institute of Technology Guwahati, North Guwahati, Assam 781039, India.
Herein, an organocatalytic asymmetric desymmetrizing [4+2] cycloaddition/base-mediated oxidative aromatization reaction sequence has been developed between spirophthalide 2,5-cyclohexadienones and β-methyl cinnamaldehydes. The reaction proceeds through chiral dienamine intermediate formation, and the densely functionalized spirocyclic isobenzofuranone-embedded chiral arenes were formed in high yields with excellent enantioselectivities. A 2-fold desymmetrization reaction was also performed, and the products were obtained in high enantioselectivities.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003, China.
Easily obtainable and efficient chiral -symmetric bipyridine-,'-dioxide ligands with Ni(OTf) were developed for application in catalyzing [3 + 2] cycloaddition reactions to synthesize optically active fused pyrazolidines or pyrazoline derivatives featuring three contiguous stereogenic centers by employing azomethine imines and α,β-unsaturated 2-acyl imidazoles, affording the corresponding adducts with the opposite configuration compared to previous synthetic products in 80-98% yields with 28-99% ee and >20:1 dr. In addition, subsequent amplification experiments and derivative transformations of the product further demonstrated the efficient catalytic performance of the catalyst Ni(II)-bipyridine-,'-dioxide complexes and the practicality of this synthesis methodology.
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