Access to Chiral Bridged Biaryls via Brønsted Acid-Catalyzed Asymmetric Addition of Alcohols to Fluoroalkylated Biaryl Oxazepines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

We disclose herein a chiral phosphoric-acid-catalyzed enantioselective addition reaction of alcohols to fluoroalkylated biaryl 1,3-oxoazepines, which furnished wide range bridged biaryls bearing quaternary carbon stereocenter on the seven-membered ring in high yields (up 99%) with excellent enantioselectivities 98% ee). Our method can be used for modification several natural products and bioactive molecules. Preliminary studies revealed that obtained this exhibit good vitro bioactivities against two plant pathogens.

Language: Английский

Enhanced Pyridine-Oxazoline Ligand-Enabled Pd(II)-Catalyzed Aminoacetoxylation of Alkenes for the Asymmetric Synthesis of Biaryl-Bridged 7-Membered N-Heterocycles and Atropisomers

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

A new class of binaphthyl unit-enhanced pyridine-oxazoline ligands was developed to promote the Pd-catalyzed enantioselective intramolecular 7-exo aminoacetoxylation unactivated biaryl alkenes. Biaryl-bridged 7-membered N-heterocycles bearing a chiral center were obtained in good yields with excellent enantioselectivities (up 99:1 er). Computational investigations on series biaryl-bridged rings provided insights into rotational barrier potentially unit by substituent effect including heteroatom, protecting group, and center. The kinetic resolution racemic axially biaryls via alkenes has also been achieved, affording previously inaccessible both axis, as well amino alcohols.

Language: Английский