Organophotoredox-Driven Three-Component Synthesis of β-Trifluoromethyl β-Amino Ketones

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

In this work, we present a photoredox three-component reaction that enables the synthesis of medicinally relevant β-trifluoromethyl β-amino ketones from N-trifluoroethylhydroxylamine derivative, styrenes and DMSO. Remarkably, fluoromethyl, difluoromethyl pentafluoroethyl analogues are also accessed using same conditions. The mechanistic investigations, including radical trapping experiments, cyclic voltammetry, Stern-Volmer quenching studies isotope labelling experiments support photoinduced radical/polar crossover Kornblum-type oxidation mechanisms. Finally, applicability organic skeletons is showcased by notable derivatization reactions.

Language: Английский

Energy Transfer Catalysis Enabled 2,2,2‐Trifluoroethoxy‐Amination of Olefins

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

Published: May 6, 2025

A thioxanthone‐catalyzed 2,2,2‐trifluoroethoxyamination of olefins is developed via the formation corresponding alkoxy and iminyl radicals using unprecedented, easily prepared, bench‐stable oxime ethers as bifunctional reagents. To bypass possible side reactions (1,2‐Hydrogen Atom Transfer (HAT), H‐abstraction, β‐scission), high reactivity radical fine‐tuned to promote selective challenging a COCH 2 CF 3 bond. This reaction, involving triplet energy transfer process, allows concomitant CN COAlk bond, so far uncharted, ether Hence, difunctionalization myriad electron‐rich alkenes selectively afforded anti‐Markovnikov products with large functional group tolerance (44 examples, up 77% yield), offering straightforward complementary regioselectivity compared existing approaches for 2,2,2‐trifluoroethanol. Post‐functionalization mechanistic investigations provided key insights into reaction mechanism this transformation.

Language: Английский

Photocatalyst-free Light-Mediated Three-Component Alkoxy-, Hydroxy-, and Azidotrifluoromethylation of Alkenes

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6660 - 6665

Published: Jan. 1, 2024

A photocatalyst-free method enables efficient alkene difunctionalization in CF 3 -rich organic environments using accessible starting materials. This protocol is applicable for the synthesis of alkoxy, hydroxy, and azido derivatives.

Language: Английский