Visible-Light-Mediated Vicinal Dihalogenation of Unsaturated C–C Bonds Using Dual-Functional Group Transfer Reagents

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 31547 - 31559

Опубликована: Ноя. 5, 2024

The growing demand for chemical production continues to drive the development of sustainable and efficient methods introducing molecular complexity. In this context, exploration unconventional functional group transfer reagents (FGTRs) has led significant advancements in practical atom-efficient synthetic protocols. Aiming advance field valuable organic synthesis, herein we report successful carbon-based, bench-stable, modular, inexpensive implemented dual halogen unsaturated hydrocarbons via photocatalytic activation based on a radical-polar crossover mechanism. This method beneficially enables vicinal dichlorination, dibromination, bromo-chlorination reactions olefins, offering alternatives use toxic binary halogens. Detailed mechanistic studies, combining experimental, spectroscopic, theoretical investigations, revealed distinctive single-electron reduction FGTR. process triggers mesolytic carbon–halogen bond cleavage, followed by radical 1,2-halide rearrangement, leading continuous generation dihalogen species reaction medium. wide applicability developed protocol is demonstrated through an extensive scope molecules, including additional operations strain-release dihalogenation.

Язык: Английский

Visible-Light-Driven Catalytic Dehalogenation of Trichloroacetic Acid and α-Halocarbonyl Compounds: Multiple Roles of Copper

ACS Catalysis, Год журнала: 2025, Номер 15(5), С. 3873 - 3881

Опубликована: Фев. 19, 2025

Herein, we report the reaction development and mechanistic studies of visible-light-driven Cu-catalyzed dechlorination trichloroacetic acid for highly selective formation monochloroacetic acid. Visible-light-driven transition metal catalysis via an inner-sphere pathway features dual roles species in photoexcitation substrate activation steps, a detailed understanding their is crucial further light-driven catalysis. This catalytic method, which environmentally desired ascorbic as hydrogen atom source water/ethanol solvent, can be applied to dehalogenation variety halocarboxylic acids amides. Spectroscopic, X-ray crystallographic, kinetic have revealed mechanism copper photoexcitation, thermal first C–Cl bond, excited-state second bond chlorine transfer.

Язык: Английский

Recent advances in electrochemical difunctionalization of alkenes and alkynes for the synthesis of organohalides

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5306 - 5324

Опубликована: Янв. 1, 2024

This review summarizes recent achievements in electrosynthesis of organohalides through difunctionalization alkenes and alkynes provides insights into future directions for the development field.

Язык: Английский