Organoboron Mediated Homolytic Aromatic Substitution of N-Methoxypyridinium Salts

<p>The monoalkylation of N-methoxypyridinium salts with alkyl radicals generated from alkenes (via hydroboration with catecholborane), alkyl iodides (via iodine atom transfer) and xanthates is reported. The reaction proceeds under neutral conditions since no acid is needed to activate the heterocycle and does not require the use of an external oxidant. A rate constant for the addition of a primary radical to N-methoxylepidinium >107 M–1 s–1 was experimentally determined. This rate constant is more than one order of magnitude larger than the one measured for the addition of primary alkyl radical to protonated lepidine demonstrating the remarkable reactivity of methoxypyridinium salts towards radicals. The reaction could be extended to a three component carbopyridinylation of electron rich alkenes including enol esters, enol ethers and enamides.</p>

Organoboron Mediated Homolytic Aromatic Substitution of N-Methoxypyridinium Salts

<p>The monoalkylation of N-methoxypyridinium salts with alkyl radicals generated from alkenes (via hydroboration with catecholborane), alkyl iodides (via iodine atom transfer) and xanthates is reported. The reaction proceeds under neutral conditions since no acid is needed to activate the heterocycle and does not require the use of an external oxidant. A rate constant for the addition of a primary radical to N-methoxylepidinium >107 M–1 s–1 was experimentally determined. This rate constant is more than one order of magnitude larger than the one measured for the addition of primary alkyl radical to protonated lepidine demonstrating the remarkable reactivity of methoxypyridinium salts towards radicals. The reaction could be extended to a three component carbopyridinylation of electron rich alkenes including enol esters, enol ethers and enamides.</p>

The role of photocatalysts in radical chains in homolytic aromatic substitution, radical addition to olefins, and nucleophilic radical substitution mechanisms

Initiation, propagation and chain termination steps in oxidative and reductive quenching cycles for the photoinitiated perfluoroalkylation reaction of an olefin.

Ground State Cross-Coupling of Haloarenes with Arenes Initiated by Organic Electron Donors, Formed in situ: An Overview

Many reactions have been discovered that lead to coupling of haloarenes to arenes using potassium tert-butoxide as the base, and one of a variety of organic compounds as an additive. The organic additive reacts with the base to form a strong organic electron donor in situ that initiates a base-induced homolytic aromatic substitution (BHAS) coupling reaction, by converting the haloarene into an aryl radical. This brief report presents an overview of the wide range of organic additives that can be used, and the organic electron donors that they form.

Silyl radical initiated radical cascade addition/cyclization: synthesis of silyl functionalized 4H-pyrido[4,3,2-gh]phenanthridin-5(6H)-ones

A cyclization cascade initiated by the addition of a silyl radical to an electron-deficient carbon–carbon double bond of N-arylacrylamides, followed by intramolecular cyano group insertion and homolytic aromatic substitution has been reported.

α-Arylation of alkylamines with sulfonylarenes through a radical chain mechanism

A radical chain, conducted by a sulfonyl radical in a homolytic aromatic substitution mechanism, makes it possible to promote α-arylation of alkylamines with sulfonylarenes just by using a substoichiometric amount of a tert-butoxy radical precursor.