Enantioselective Pd- and Cu-Catalyzed Hydrofunctionalization of Methylenecyclopropanes via a Distal C–C Bond Cleavage

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

Published: Jan. 28, 2025

The enantioselective ring-opening reactions of methylenecyclopropanes (MCPs) involving C–C bond activation via oxidative addition transition metals have been rarely reported. Here, we disclose a Pd/Cu-catalyzed enantio- and regioselective coupling between cyclic imino esters MCPs to produce α-allylated 2H-pyrrole derivatives. In this reaction, azomethine ylide formed by chiral copper catalyst with ketimine ester would serve as nucleophile react activated palladium catalysis. This bimetallic system exhibited broad substrate scope high regio- enantioselectivities.

Language: Английский

Palladium-Catalyzed Enantioselective Ring-Opening/Cyanation of Cyclobutanones

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

Published: April 9, 2025

Palladium-catalyzed asymmetric transformations involving cyanide anions remain a challenge due to the strong affinity between and palladium, which induces alterations in coordination sphere of palladium center. Herein, palladium-catalyzed enantioselective cyanation is achieved via ring-opening/cross-coupling process aryl halide-tethered cyclobutanones Zn(CN)2. This reaction demonstrated exhibit broad substrate scope robust enantioselectivity. The synthetic utility highlighted by converting product into amide, carboxylic acid, ester without racemization.

Language: Английский