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

Ether-Directed Enantioselective C(sp²)–H Borylation for the Synthesis of Axially Chiral Biaryls

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

Published: April 9, 2025

We report an ether-directed enantioselective C(sp2)-H borylation catalyzed by a chiral bidentate boryl ligand (CBL)/iridium system for constructing axially biaryls. This method delivered diverse biaryls with good to high enantioselectivities, accommodating varied electronic and steric substituents on the aryl rings. Gram-scale synthesis downstream transformations of C-B bond underscored its practicality.

Language: Английский