Enantioselective desymmetrization of meso-aziridines and meso-epoxides with various nucleophiles by organocatalysis has emerged as a cutting-edge approach in recent years. This review summarizes the origin and recent developments of enantioselective desymmetrization of meso-aziridines and meso-epoxides in the presence of organocatalysts.
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http://dx.doi.org/10.3762/bjoc.9.192 | DOI Listing |
J Am Chem Soc
January 2025
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Ni-catalyzed asymmetric reductive cross-coupling reactions provide rapid and modular access to enantioenriched building blocks from simple electrophile precursors. Reductive coupling reactions that can diverge through a common organometallic intermediate to two distinct families of enantioenriched products are particularly versatile but underdeveloped. Here, we describe the development of a bis(oxazoline) ligand that enables the desymmetrization of -anhydrides.
View Article and Find Full Text PDFChemistry
January 2025
Beijing Normal University, College of Chemistry, Xiejiekou NO.19, 100875, Beijing, CHINA.
Optically pure monosubstituted [n]paracyclophanes are promising candidates for material synthesis, asymmetric catalysis, and drug discovery. Thus far, only a few catalytic asymmetric synthesis processes have been reported for assessing these stained atropisomers. In this study, we describe a highly enantioselective synthesis of monosubstituted [n]paracyclophanes by combining desymmetrization and kinetic resolution.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012, India.
Despite tremendous progress of dienamine catalysis along with its application in enantioselective synthesis over nearly two decades, certain limitations, especially with respect to the regioselectivity in the dienamine generation step, continue to persist. To overcome these shortcomings of classical dienamine catalysis, we now introduce the concept of alkoxy-directed dienamine catalysis and apply it to the enantioselective arene construction by desymmetrizing -enediones through [4 + 2]-cycloaddition. Catalyzed by a diphenylprolinol silyl ether, this reaction utilizes γ-alkoxy α,β-unsaturated aldehydes as the substrate and proceeds in a highly regioselective fashion through the intermediacy of δ-alkoxy dienamine.
View Article and Find Full Text PDFOrg Lett
January 2025
College of Materials and Energy, South China Agricultural University, 510642 Guangzhou, China.
We report herein a robust enantioselective ring opening coupling of oxabenzonorbornadienes via Pd(II)-catalyzed domino cyclization of alkynylanilines, which features the formation of three covalent bonds and two contiguous stereocenters with excellent enantio- and diastereoselectivity and a broad substrate scope. The good functional group tolerance of this domino desymmetrization strategy enables efficient late-stage transformation of natural product-derived alkynylanilines. The resulting indolated dihydronaphthols could serve as a valuable platform to streamline the diversity-oriented synthesis of other valuable enantioenriched tetrahydronaphthalene derivatives.
View Article and Find Full Text PDFOrg Lett
January 2025
College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, China.
The enantioselective synthesis of P(V)-stereogenic compounds has emerged as an interesting research topic primarily due to their significant biological activity and broad application prospects. Herein, we disclose a method for the construction of P(V)-stereogenic compounds from prochiral phosphinamides and aryl iodides via palladium- and chiral norbornene-catalyzed desymmetric annulation. The P(V)-stereogenic compounds were formed with a broad scope with excellent enantiomeric excesses.
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