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

Hypervalent Iodine Mediated Ring-Opening 1,3-Difluorination of Benzylidenecyclopropanes

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: July 25, 2024

Abstract 1,3-Difluorinated compounds are characterized by their unique conformation, influenced 1,3-dipolar minimization effects. However, synthetic methods relatively limited. Here, a ring-opening 1,3-difluorination of benzylidenecyclopropanes (BCPs) using HF·Py, mediated an electron-poor hypervalent iodine reagent, which is generated in situ the oxidation o-nitroiodobenzene with mCPBA described. The protocol features mild reaction conditions, good functional group tolerance, and moderate to yields. Additionally, utility this method showcased further transformations olefin allylic fluoride motif.

Language: Английский