Catalytic Desymmetrization of <i>meso</i>-Aziridines with Benzofuran-2(3<i>H</i>)‑Ones Employing a Simple In Situ-Generated Magnesium Catalyst

The first example of catalytic desymmetrization of <i>meso</i>-aziridines with benzofuran-2­(3<i>H</i>)-ones is realized by employing a magnesium catalyst utilizing BINOL as a simple and commercially available chiral ligand. Both of the enantiomers of the ring-opening product could be easily accessed by employing (<i>R</i>)- or (<i>S</i>)-BINOL as chiral ligand, respectively. A variety of enantioenriched 3,3-disubstituted benzofuran-2­(3<i>H</i>)-ones containing multiple linear continuous stereocenters were obtained with moderate to good yields, diastereo- and enantioselectivities

Enantioselective Dearomative Arylation of Isoquinolines

The C1-substituted tetrahydroisoquinolines and 1,2-dihydroisoquinoline constitute an important group and are interesting structural motifs found in many natural products and pharmaceuticals. In this context, a phosphoric-acid-catalyzed enantioselective dearomative arylation of isoquinolines was realized, providing the chiral dihydroisoquinolines with indole substituents at the C1-position in good results (up to >99% yield and 97% ee). The reaction features mild reaction conditions and operational simplicity, which make it an attractive approach to the discovery of biologically interesting α-indolisoquinolines

Catalytic Asymmetric [3 + 2] Cyclization Reactions of 3‑Isothiocyanato Oxindoles and Alkynyl Ketones Via an in Situ Generated Magnesium Catalyst

A highly enantioselective formal [3 + 2] cycloaddition reaction between 3-isothiocyanato oxindoles and alkynyl ketones is reported for the first time. An oxazoline–OH type chiral ligand derived from <i>o</i>-hydroxy-phenylacetic acid is employed to generate an effective magnesium catalyst in the current cyclization reaction and give serials of chiral spirooxindoles with good chemical yields and enantioselectivities

β‑l‑Rhamnosylation and β‑d‑Mannosylation Mediated by 4‑<i>O</i>‑Ester Groups in a Weakly Nucleophilic Environment

eq-4-O-Acyl group directed β-rhamnosylation and β-mannosylation are achieved in a carborane or BARF anion formed weakly nucleophilic environment with the assistance of a 2,3-orthocarbonate group. The 4-O-acyl group plays a critical role in directing the β-selectivity, and the weakly coordinating anion is essential to amplify this direction. The orthocarbonate group could be readily removed with 1,3-propanediol in the presence of BF3·Et2O