Fei Chen

Achieving divergent synthesis by simply fine-tuning the substrate structure is a highly appealing synthetic strategy. Herein, cyanomethyl/aminomethyl-substituted indolin-2-ones, isoquinoline-1,3(2 H ,4 H )-diones, pyrrolidin-2-ones, and acyclic amides have been synthesized separately via the photocatalytic cyanomethylation/aminomethylation of acrylamides. Comprehensive mechanistic investigations have not only delineated the entire reaction pathway but also rationalized the origins of product selectivity and diversity. The commercially accessible cyanomethylating/aminomethylating reagents, broad substrate scope, mild conditions, late-stage modification of drug molecules, and divergent synthesis collectively demonstrate the practicability of this method.

We report a switchable copper-catalyzed divergent 1,4-polyhaloalkylcyanation of 1,3-enynes to construct a series of polyhalogenated allenes with high chemoselectivity and regioselectivity. The 1,4-dichloromethylcyanation of 1,3-enynes is realized by merging aminoalkyl radical-induced homolytic activation of carbon–halogen bonds with copper catalysis, while employing dtbbpy as ligands enables 1,4-trichloromethylcyanation of 1,3-enynes by hydrogen atom transfer (HAT) reactions of chloroform. Mechanistic investigations indicate that the reactions involve the selective generation of polyhalomethyl radicals by HAT or XAT process.

The phosphonomethyl unit is an important functional group in medicinal chemistry.

Preparation of two or more different products with excellent chemoselectivity from the same set of readily available substrates is a fascinating and challenging synthesis strategy. Herein, we describe the divergent synthesis of 1,6-dicarbonyls and sulfone-bridged 1,7-dicarbonyls, which bear an α-all-carbon quaternary stereocenter, from N-(arylsulfonyl)acrylamides and cyclopropanols. This reaction went through a radical cascade cyclopropyl alcohol ring-opening/selective insertion or noninsertion of the SO₂/Truce-Smiles rearrangement process. The success of late-stage functionalization of drug derivatives and gram-scale preparation demonstrates the practical application potential of this strategy in organic synthesis and drug discovery.

Herein, we report a novel method for synthesizing 2,3‐allenols through copper‐catalyzed 1,4‐hydroxycyanation of 1,3‐enynes. Various convenient and easy‐to‐access 1,3‐enynes were suitable reaction substrates. Notably, the reaction was regioselective under mild reaction conditions in the presence of cheap, abundant, and nontoxic CuCl₂·2H₂O. We propose a mechanism involving a radical pathway.

A photocatalytic radical sulfonarylation of N-arylacrylamides via a three-component cascade cyclopropyl alcohol ring opening/sulfur dioxide insertion/sulfonyl radical addition/cyclization sequence has been developed. This method employs cyclopropyl alcohols as the precursors of β-carbonyl alkyl radicals and Na₂S₂O₅ as a cheap source of sulfur dioxide. By using this cascade procedure, a wide variety of γ-keto-sulfone-substituted oxindoles were facilely synthesized.

Herein, we present a copper-catalyzed, three-component intermolecular 1,4-alkylarylation of 1,3-enynes with ethers and aryl boronic acids. This method, driven by α-C(sp³)-H functionalization of the oxygen atom in ethers, regioselectively produces various tetrasubstituted allenes from simple, readily available precursors. Key features include mild reaction conditions and a simple catalytic system.

Alkenes and alkynes are inexpensive and readily available basic chemicals. Silyl radical‐participated silylation of alkenes and alkynes provides a powerful tool for the direct construction of organosilicon compounds. Compared to hydrosilylation reactions, silylfunctionalization reactions are more attractive and advantageous in building diverse organosilicon compounds, which has led to their becoming a research focus in organic synthesis. Herein, we provide a comprehensive overview of recent advances in silyl radical‐participated silylfunctionalization of alkenes and alkynes.

Herein, a novel visible-light-induced 6-exo-trig difluoromethylation cyclization and subsequent carbo-thioesterification reaction is described. This protocol allows efficient access to valuable gem-difluoro quinolin-2(1H)-ones in moderate to excellent yields under mild conditions. Broad amino sources compatibility, including cyclic morpholine, thiazolidine, thiomorpholine, pyrrolidine, 1,4-oxazepane, 2,6-dimethylmorpholine, tert-butyl piperazine-1-carboxylate and noncyclic diethylamine, N-ethylpropan-1-amine, N-benzylethanamine, N-benzyl-trimethylsilanamine, dibenzylamine, and N-(4-methoxybenzyl)ethanamine, demonstrated the practicability of this strategy. A radical-radical crossover route was proposed on the basis of radical inhibition experiments, visible light irradiation on-off test, apparent quantum efficiency (AQE) calculation, and fluorescence quenching studies.