FeCl₃-Catalyzed Intermolecular Formal [8π+2σ] Cycloaddition of Azaheptafulvene with Bicyclo[1.1.0]butanes for the Synthesis of Cycloheptatriene-Fused 2-Azabicyclo[3.1.1]heptanes

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

Published: April 8, 2025

Higher-order cycloadditions are a simple and effective strategy for constructing significant medium-sized architectures. Azaheptafulvenes reacting with readily accessible bicyclo[1.1.0]butanes (BCBs) through FeCl3-promoted intermolecular formal [8π+2σ] cycloaddition reactions to access cycloheptatriene-fused 2-azabicyclo[3.1.1]heptanes have been developed. This new reaction tolerated wide range of azaheptafulvenes BCBs. Furthermore, the amplification experiment synthetic transformations adducts, including modifications marketed drugs, further highlighted their practicalities. Control experiments DFT calculations suggest that diastereoselective product formation may involve stepwise pathway.

Language: Английский

Structure-Dependent, Switchable Alder-Ene/[2π + 2σ] Cycloadditions of Vinyl Bicyclo[1.1.0]butanes with α-Ketoesters Enabled by Palladium Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

A structure-dependent, palladium-catalyzed switchable alder-ene/[2π + 2σ] cycloaddition of VBCBs with α-ketoesters has been reported. variety cyclobutenes and 2-oxabicyclo[2.1.1]hexanes have efficiently achieved in good to excellent yields through strain-release-driven alder-ene reactions [2π cycloadditions, respectively. The potential this method is illustrated by the scale-up reaction diverse postsynthetic transformations obtained cyclic scaffolds. Additionally, mechanism origins chemoselectivity probed computational studies.

Language: Английский