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Overestimated Halogen Atom Transfer Reactivity of α-Aminoalkyl Radicals.

Halogen atom transfer (XAT) is a versatile method for generating carbon radicals. Recent interest has focused on α-aminoalkyl radicals as potential XAT reagents, previously reported to exhibit reactivity comparable to tin radicals. Utilizing an …

Characterization and Monitoring of Transient Enamine Radical Intermediates in Photoredox/Chiral Primary Amine Synergistic Catalytic Cycle.

Enamine-derived radicals are crucial intermediates in singly occupied molecular orbital (SOMO) catalysis. However, observing them directly is elusive and remains a long-standing challenge. Here, an advanced time-resolved electron paramagnetic …

Direct Observation of All Open-Shell Intermediates in a Photocatalytic Cycle.

Molecular photocatalysis has shown tremendous success in sustainable energy and chemical synthesis. However, visualizing the intricate mechanisms in photocatalysis is a significant and long-standing challenge. By employing our recently developed …

The Stereochemistry of the Reactions between Palladacycle Complexes and Primary Alkyl Iodides.

As an important elementary step in organometallic chemistry, the alkylation reaction of palladacycle complexes and alkyl halides has attracted much attention in recent years due to their presence as key step in palladium catalyzed C-H alkylation …

DFT Study on the Mechanism of 4,4′-Bipyridine-Catalyzed Nitrobenzene Reduction by Diboron(4) Compounds.

Diboron(4) compounds serve as useful reagents for borylation, diboration, and reduction in organic synthesis. A variety of pyridine derivatives have been found capable of activating diboron(4) compounds, and different reaction mechanisms have been …

Aromatization Modulates the Activity of Small Organic Molecules as Promoters for Carbon– Halogen Bond Activation.

The combination of small organic molecules and a base serves as a unique system for the activation carbon– halogen bonds in haloarenes by single electron transfer (SET). However, most of the molecules employed as promoters only allow for the …

*N*-Methylanilines as Simple and Efficient Promoters for Radical-Type Cross-Coupling Reactions of Aryl Iodides.

Activation of the carbon– halogen bonds in aryl halides is a key step in transition-metal-free cross-coupling reactions. In this paper, a new and efficient radical initiation system for the activation of iodoarenes to produce aryl radicals was …

Revisiting the Radical Initiation Mechanism of the Diamine-Promoted Transition-Metal-Free Cross-Coupling Reaction.

Radical chain reactions leading to C– C bond formation are widely used in organic synthesis, and initiation of the radical chain process usually requires thermolabile radical initiators. Recent studies on transition-metal-free cross-coupling …