BrCF2CN for photocatalytic cyanodifluoromethylation

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 7, 2025

Considering the unique electronic properties of CF2 and CN groups, CF2CN group has significant potential in drug agrochemical development, as well material sciences. However, incorporating a remains considerable challenge. In this work, we disclose use bromodifluoroacetonitrile (BrCF2CN), cost-effective readily available reagent, radical source for cyanodifluoromethylation alkyl alkenes, aryl alkynes, (hetero)arenes under photocatalytic conditions. This protocol demonstrates an exceptionally broad substrate scope remarkable tolerance to various functional groups. Notably, alkynes predominantly provides sterically hindered thermodynamically unfavorable outcome, (hetero)arene C-H bonds are directly amenable without pre-functionalization. Here, authors report (BrCF2CN)

Language: Английский

An Atomically Dispersed Mn Photocatalyst for Vicinal Dichlorination of Nonactivated Alkenes

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

Published: March 25, 2025

A novel Mn-based single-atom photocatalyst is disclosed in this study, designed for the dichlorination of alkenes to achieve vicinal dichlorinated products using N-chlorosuccinimide as a mild chlorinating agent, which have widespread applications pest controlling agents, polymers, flame retardants, and pharmaceuticals. In developing innovative catalyst, we achieved atomic dispersion Mn on aryl-amino-substituted graphitic carbon nitride (f-C3N4). This marks first instance heterogeneous version, offering an operationally simple, sustainable, efficient pathway alkenes, including drugs, bioactive compounds, natural products. material was extensively characterized by techniques such UV-vis spectroscopy, X-ray absorption near-edge structure (XANES), extended fine (EXAFS), high-resolution transmission electron microscopy (HR-TEM), photoelectron spectroscopy (XPS), magic-angle spinning (MAS), solid-state nuclear magnetic resonance (ssNMR) understand it at level. Furthermore, mechanistic studies based multiscale molecular modeling, combining classical reactive dynamics (RMD) simulations quantum chemistry (QC) calculations, illustrated that controlled formation Cl radicals from situ formed Mn-Cl bond responsible reaction alkenes. addition, gram-scale reusability tests were also performed demonstrate applicability approach industrial scale.

Language: Английский

Ball‐Milling‐Promoted Copper‐Catalyzed Solid‐State Radical C–H Difluoroalkylation Reactions

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

A mechanochemical strategy for promoting copper‐catalyzed solid‐state radical C–H difluoroalkylation reactions has been devised. Compared to traditional solution‐based methods, this mechanoredox approach offers enhanced ease of handling, greater cleanliness, and improved sustainability the synthesis difluoroalkylated indoles, which constitute crucial structural motifs in contemporary drug discovery. The underlying reaction mechanism is investigated through meticulous step‐by‐step control experiments that highlighted substantial influence conditions. versatility protocol demonstrated by its applications complex natural products derivatives.

Language: Английский