- Radical Hydroarylation of Functionalized Olefins and Mechanistic Investigation of Photocatalytic Pyridyl Radical Reactions
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We report the photoredox alkylation of halopyridines using functionalized alkene and alkyne building blocks. Selective single-electron reduction of the halogenated pyridines provides the corresponding heteroaryl radicals, which undergo anti-Markovnikov addition to the alkene substrates. The system is shown to be mild and tolerant of a variety of alkene and alkyne subtypes. A combination of computational and experimental studies support a mechanism involving proton-coupled electron transfer followed by medium-dependent alkene addition and rapid hydrogen atom transfer mediated by a polarity-reversal catalyst.
- Seath, Ciaran P.,Vogt, David B.,Xu, Zihao,Boyington, Allyson J.,Jui, Nathan T.
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supporting information
p. 15525 - 15534
(2018/11/23)
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- A dimethacrylate cross-linker cleavable under thermolysis or alkaline hydrolysis conditions: Synthesis, polymerization, and degradation
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We develop a new platform based on 2,6-pyridinediethanol diesters for introducing polymer degradability under thermolysis or alkaline hydrolysis conditions, with the latter being rare in polymers. Such labile diesters can be cross-linkers, bifunctional initiators and inimers. We demonstrate the power of this platform through the synthesis of the 2,6-pyridinediethanol dimethacrylate cross-linker, its controlled (co)polymerization, and the thermal and hydrolytic cleavage of its (co)polymers.
- Elladiou, Marios,Patrickios, Costas S.
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supporting information
p. 3135 - 3138
(2016/02/23)
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