Radical-mediated alkoxypolyhaloalkylation of styrenes with polyhaloalkanes and alcohols via C(sp³)–H bond cleavage

Abstract

We have developed a new radical-mediated alkoxypolyhaloalkylation of styrene with polychloroalkanes and alcohols for the facile synthesis of complex polyhaloalkanes. 4-Methoxybenzenediazonium tetrafluoroborate is a good radical initiator for this transformation....

Radical Relay Trichloromethylacylation of Alkenes through N-Heterocyclic Carbene Catalysis

“…7 These transformations convert readily available starting materials to highly valuable and complex molecules in a single step. Nevertheless, trichloromethylative difunctionalization has been limited, 8 primarily because the Kharasch reaction competes with the target reaction due to the weak C−X bond in CXCl 3 . Therefore, a mechanistically different catalysis for the key final bond forming sequence is required to realize the trichloromethylative difunctionalization of alkenes.…”

Branching out: redox strategies towards the synthesis of acyclic α-tertiary ethers

“…Recently, Ouyang & Li achieved the alkoxypolyhaloalkylation of styrenes using a similar catalytic manifold. 234 Upon thermal decomposition, an aryl diazonium salt generated the corresponding aryl radical which enacted hydrogen atom abstraction from polyhaloalkanes such as chloroform. Following radical addition and oxidation, a variety of polyhalogenated a-tertiary ethers were formed.…”

Synthesis of β-Polychlorinated Alkynes Enabled by Copper-Catalyzed Multicomponent Reaction

“…Recently, another photoredox route achieving halogenation of alkenes utilizing chloroform and chlorides as polychlorinated sources was reported by Zhu and coworks . Furthermore, Luo, Chu, Doyle, and Li demonstrated that varieties of nucleophiles could be introduced onto the alkenes enabled by iron- or copper-catalyzed radical processes respectively, wherein, the stoichiometric amount of oxidants and high temperature (100 °C) were usually employed. More recently, Ohmiya and Nagao reported a N -Heterocyclic carbene catalysis enabling a radical relay trichloromethylacylation of alkenes (Scheme c) .…”