Visible light promoted polyhalomethylation of alkenes: alkylation and cyclization

Abstract

We report a visible light promoted carbochloromethylation of 2-bromomethyl acrylate and N-arylmethacrylamide, and a series of trihalomethyl substituted allylic acid esters and indolone derivatives were synthesized. The reaction used common...

Electrophotocatalytic tri- or difluoromethylative cyclization of alkenes

“…S9 and S10†). As a result, neither the ground-state nor photoexcited eosin Y would be preferentially oxidized at the anode, excluding both the electron-primed photocatalytic mechanism 19,21 a , b ,22 and oxidative quenching cycle 32 -involved electrophotocatalytic pathway. It is established that 2a could significantly attenuate eosin Y fluorescence in a Stern–Volmer quenching experiment (Fig.…”

“…Eosin Y is a versatile photosensitizer, 31 and while it is a frequently used photoreductant, 32 it could function as a photooxidant as well. 33,34 Cyclic voltammetry (CV) tests indicated that eosin Y has an oxidation potential of 1.00 V vs. Ag/AgCl (Scheme 3d and Fig.…”

Rapid Access to γ,γ‐Dichloroketones via Radical‐Induced Dichloromethylation and Concomitant 1,2‐Aryl Migration of Allylic Alcohols with CHCl3

“…In addition, it can also serve as a flexible precursor for various halogenated groups in organic synthesis. Chloroform selectively produces trichloromethyl radicals in the presence of peroxides, [12] copper catalysts, [13] or photocatalysts [14] . Subsequent studies have found that chloroform can also selectively produce dichloromethyl radicals under appropriate conditions [15] .…”

“…ces trichloromethyl radicals in the presence of peroxides, [12] copper catalysts, [13] or photocatalysts. [14] Subsequent studies have found that chloroform can also selectively produce dichloromethyl radicals under appropriate conditions. [15] For example, the Doyle research group utilized copper catalysis to achieve the alkylation peroxidation of olefin with TBHP and CHCl 3 to efficiently construct various α-tert butyl peroxide-β-dichloromethyl substituted alkanes.…”

The polychloromethylation/acyloxylation of 1,6-enynes with chloroalkanes and diacyl peroxides through dual-role designs

“…Distinctive polychloromethylated molecules containing di- or trichloromethyl moieties are significant subclasses that are widely found in pharmaceuticals, pesticide molecules, and biologically active natural products. 1 Among them, the polychloromethyl moiety is usually the critical functional unit for providing effective activity. Given the importance of polychloromethyl compounds, chemists have developed several approaches for realizing polychloromethylation, including the use of novel halogenating enzymes to catalyze the polychloromethylation of unactivated aliphatic carbon centers, 2 peroxide-induced halogenated addition to alkenes, 3 the nucleophilic addition of chloroform or dichloromethane to alkenes in the presence of strong bases, 4 and so on.…”