Enantioselective Dearomative [2π + 2σ] Photocycloaddition of Naphthalene Derivatives with Bicyclo[1.1.0]butanes Enabled by Gd(III) Catalysis

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

Published: March 28, 2025

The cycloaddition reactions of bicyclo[1.1.0]butanes with alkenes, imines, nitrones, or aziridines have served as an efficient platform to create conformationally restricted saturated bicyclic scaffolds. However, the use readily available aromatics in such reactions, especially asymmetric manner, remains underexplored. Herein, we report a highly regio- and enantioselective dearomative [2π + 2σ] photocycloaddition reaction between naphthalene derivatives bicyclo[1.1.0]butanes, enabled by Gd(III) catalysis. Bicyclo[1.1.0]butanes naphthalenes adorned diverse array functional groups are well-tolerated under mild conditions, affording enantioenriched pharmaceutically important bicyclo[2.1.1]hexanes 30–96% yields 81–93% ee 12:1 → >20:1 rr. synthetic versatility this is further demonstrated facile removal directing group derivatizations dearomatized product. UV–vis absorption spectroscopy studies suggest involvement excited species process.

Language: Английский

Ag(I)-Catalyzed Tandem Cyclization–Cycloaddition–Isomerization Reaction of 2-Alkynylbenzaldoxime with Bicyclobutane: A Route to Multiply Substituted Cyclobutanols

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

Published: April 1, 2025

Multiply substituted cyclobutanols are pivotal synthetic intermediates for constructing complex molecular architectures via ring-opening strategies. The development of efficient methods these valuable building blocks has garnered significant interest in the chemical community. In this work, we have described a novel silver(I)-catalyzed tandem cyclization–cycloaddition–isomerization sequence with bicyclobutanes and 2-alkynylbenzaldoximes, which offered an effective route to multiply cyclobutanols. This protocol features mild conditions, remarkable stereospecificity, broad substrate scope, excellent functional group tolerance. addition, application potential reaction was readily proven by its high efficiency reactants bearing biological moieties scale-up experiments.

Language: Английский

Lewis Acid-Catalyzed Enantioselective (4 + 3)/Thia-(3 + 2) Cycloadditions of Bicyclobutanes and Enaminothiones: Catalyst-Directed Divergent Synthesis of Bridged Sulfur Heterocycles

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7877 - 7890

Published: April 28, 2025

Language: Английский