Diradical Generation via Relayed Proton-Coupled Electron Transfer

Abstract

Diradical generation followed by radical–radical cross-coupling is a powerful synthetic tool, but its detailed mechanism has yet to be established. Herein, we proposed and confirmed a new model named relayed proton-coupled electron transfer (relayed-PCET) for diradical generation, which could open a door for new radical–radical cross-coupling reactions. Quantum mechanics calculations were performed on a selected carbene-mediated diradical cross-coupling reaction model and a designed model, and the exact electronic structural changes during the radical processes have been observed for the first time.

NHC‐Organocatalysed Hydroacylation of Unactivated or Weakly Activated C−C Multiple Bonds and Ketones

“…The exact electronic structural changes during the radical processes in selected carbene-mediated diradical cross-coupling reactions have been studied utilizing Quantum mechanical studies. [30] Xu and co-workers demonstrated a combination of tertiary amine catalysis and NHC catalysis which were doable through sequential N-allylation/hydroacylation reaction. The one-pot reaction starts with N-allylation of indole-2-carbaldehyde 25 using Morita-Baylis-Hillman (MBH) carbonates 26 in the presence of 1,4-phthalazinediyl, (DHQD)2PHAL to give chiral Nallylated adduct 27 (Scheme 5).…”

“…have introduced relayed proton‐coupled electron transfer (relayed‐PCET) for diradical generation. The exact electronic structural changes during the radical processes in selected carbene‐mediated diradical cross‐coupling reactions have been studied utilizing Quantum mechanical studies [30] …”

Synthesis of Pincer type carbene and their Ag(I)-NHC complexes, and their Antimicrobial activities

“…One feasible route for the adjustment of complexes with protic pNHC ligands is the oxidative supplementation of [11] N-alkyl halogen azoles [12] or unsubstituted azoles to different kind low-valent transition metals, such as Ni, Pd, and Pt. As a proton resource, this reaction gives pNHC complexes of type I, as an example [13].…”

“…Additionally, aryl bonding and two silver centers contributed to their antimicrobial action. Synthesized compounds were investigated with different techniques, such as FTIR, 1 H-NMR, 13 C-NMR, TGA, SEM, XRD, and elemental analysis [43].…”

“…A pellet machine using a steel die (Desk-Top presser, Model: YLJ-24 MTI Corporation) under a pressure of ~10 tons was used to form a pellet. 1 H-NMR and 13 C-NMR spectra were recorded using a Varian As 300 Merkur spectrometer operating at 300 MHz ( 1 H-NMR) and 75 MHz ( 13 C-NMR) in CDCl 3 .…”