Metal-free, highly efficient organocatalytic amination of benzylic C–H bonds

Abstract

A new synthetic approach toward direct C-N bond formation through sp(3) C-H activation has been developed under metal-free conditions. Both primary and secondary benzylic C-H substrates could react smoothly with various amines to give only mono-amination products with good to excellent yields.

nBu4NI‐Catalyzed α‐Benzoxylation of Ketones with Terminal Aryl Alkenes

“…This substitution should occur through an attack of 4 onto the oxygen atom of the carbonyl unit of the perester to form a highly stabilized benzylic as well as a double‐heteroatom‐stabilized radical followed by the subsequent fragmentation of the tert ‐butoxy radical. Alternatively, radical 4 could be oxidized into cation intermediate 5 , similar to the reports of Yu and Zhu 3c,4f. The occurrence of having a positive charge α to a carbonyl group has already been reported,16 though such a cation is seemingly unstable.…”

Efficient imidation of C(sp3)–H bonds adjacent to oxygen atoms of aryl ethers under metal-free conditions

“…It is noteworthy that 1-methoxy-4-methylbenzene gave the methyl imidated product (3g), while the methoxy group remained intact, consistent with a previous report by Zhu's group. 13 Similarly a smooth coupling was observed for aryl ethers bearing substitution groups at different positions such as 2-Cl, 3-Cl and 4-Cl and no previous yield disparity was observed (3d, 3e and 3f). The fused bicyclic 1-methoxynaphthalene (3n) was inert during the reaction.…”

Synthesis of Structurally Diverse Benzotriazoles via Rapid Diazotization and Intramolecular Cyclization of 1,2‐Aryldiamines

“…: [33] The reaction was carried out as described in the general procedure using N- (4′′-methoxybenzyl) 13…”