Photocatalytic 1,3-Difluoroalkylcarboxylation of Alkenes by Triple Kinetic-Controlled Radical Self-Ordering

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A transition-metal-free protocol for the unsymmetrical radical 1,3-difunctionalization of alkenes has been established first time in form 1,3-difluoroalkylcarboxylation by a photocatalytic three-component reaction allyl formates, trifluoroacetanilides, and cesium formate. This employs formate as carboxylating reagent trifluoroacetanilide difluoroalkylating via C-F bond activation. As result, series previously inaccessible difluorinated adipic acid derivatives can be easily efficient prepared. Mechanism studies reveal that triple kinetic-controlled self-ordering is key to this unique reaction. sorting involves fast initiation CO2 anion its chemoselective addition reduction, followed slow generation fluoroalkyl chemo-/regioselective addition. Notably, strategy also suitable cyclic through diastereoselectively constructing two or three consecutive stereocenters.

Language: Английский

Radical‐Polar Crossover Bicyclization Enables a Modular Synthesis of Saturated Bicyclic Amines

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Abstract The rapid assembly of diverse cyclic amines from simple precursors is now considered as an ideal platform with respect to efficiency and sustainability. To date, numerous synthetic methods have been successfully developed however, most them are limited a narrow subset amines, variations in ring size often requiring different substrates distinct strategies. Furthermore, the “escape‐from‐Flatland” concept has led chemists focus on synthesis C(sp 3 )‐rich small molecules for potential drug candidates. Herein, successful realization radical‐polar crossover bicyclization reaction reported easily available cyclopropylamines substituted alkenes through photoredox catalysis. This approach introduces innovative methodology de novo collection 4/5‐, 5/5‐, 6/5‐,7/5‐, 5/6‐fused saturated bicyclic systematic modular manner excellent diastereoselectivity. work highlights utility photoinduced radical–polar bicyclization, applicability which showcased by functional group tolerance, wide substrate scopes, derivatization reactions.

Language: Английский

Catalyst-free reaction of 2-(4H-benzo[d][1,3]oxazin-4-yl)acrylates: synthesis of 1,2-dihydroquinolines and 2,3-dihydropyrroles

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(54), P. 6933 - 6936

Published: Jan. 1, 2024

Catalyst-free annulations of 2-(4

Language: Английский