Radical 1,2-Alkylarylation/Acylarylation of Allylic Alcohols with Aldehydes via Neophyl Rearrangement

A metal-free 1,2-alkylarylation of allylic alcohols with aliphatic aldehydes through concomitant radical neophyl rearrangement was developed, providing 1,2-diphenyl-3-alkyl propanones in moderate to good yields. Moreover, when cyclo­propane­carbaldehyde and aryl carbaldehydes were concerned, acylarylation was involved leading to 1,4-dicarbonyl compounds

TBAI-Catalyzed Reaction between <i>N</i>‑Tosylhydrazones and Sulfur: A Procedure toward 1,2,3-Thiadiazole

A TBAI-catalyzed reaction between <i>N</i>-tosyl hydrazone and sulfur was developed, leading to 1,2,3-thiadiazoles in moderate to good yields. It represents a facile and practical procedure to access thiadiazole under metal-free conditions. This procedure serves as an improvement for the Hurd–Mori reaction

Cs₂CO₃‑Promoted Carboxylation of <i>N</i>‑Tosylhydrazones with Carbon Dioxide toward α‑Arylacrylic Acids

A Cs₂CO₃-promoted carboxylation of <i>N</i>-tosylhydrazones and CO₂ has been developed. The reaction proceeded efficiently at 80 °C under atmospheric CO₂, gave the corresponding α-arylacrylic acids in moderate to good yields. This method was featured with (1) the employment of Cs₂CO₃ rather than ^<i>n</i>BuLi as the base; (2) a reaction temperature of 80 °C rather than −78 °C

<i>tert</i>-Butyl Peroxybenzoate-Promoted α‑Methylation of 1,3-Dicarbonyl Compounds

A <i>tert</i>-butyl peroxybenzoate (TBPB)-promoted direct α-methylation of 1,3-dicarbonyl compounds has been developed, providing α-methyl derivatives in moderate to good yields. In this procedure, TBPB plays a dual role, serving as both the methyl source and radical initiator. This work represents a key complement to the traditional α-methylation of 1,3-dicarbonyl compounds using methyl iodide

Metal-Free Cascade Oxidative Decarbonylative Alkylation/Arylation of Alkynoates with Alphatic Aldehydes

The oxidative difunctionalization of aryl alkynoates with alphatic aldehydes as a cheap and abundant alkyl radical source was developed, providing a variety of trisubstituted alkenes in moderate to good yields. In this reaction, radical decarbonylative alkylation of C-C triple bond, 1,4-aryl migration, and decarboxylation were involved under metal-free conditions

Metal-Free Radical Oxidative Annulation of Ynones with Alkanes To Access Indenones

The benzoyl peroxide (BPO) promoted carboannulation of ynones with alkanes is developed, affording a series of 2-alkyl-3-aryl indenones in moderate to good yields. The procedure involves direct functionalization of alkane C­(sp³)–H and arene C­(sp²)–H bonds under metal-free conditions, providing a favorable approach for indenone synthesis

Di-<i>tert</i>-butyl Peroxide-Promoted α‑Alkylation of α‑Amino Carbonyl Compounds by Simple Alkanes

A di-<i>tert</i> butyl peroxide (DTBP)-promoted α-alkylation of α-amino carbonyl compounds by simple alkanes is developed, proceeding through dual sp³ C–H bonds cleavage. The reaction was applicable for α-amino ketones and α-amino esters, providing a facile pathway for the α-functionalization of these substrates. The radical pathway is involved in this transformation

Copper-Catalyzed <i>N</i>‑Cyanation of Sulfoximines by AIBN

The direct copper-catalyzed <i>N</i>-cyanation of sulfoximines was achieved by using AIBN as a safe cyanide source. It represents a simple and environmentally benign procedure for the construction of the N–CN bond. Furthermore, some <i>sec</i>-amines can also be tolerated well under this procedure

Palladium-Catalyzed Multicomponent Reactions of <i>o</i>‑Alkynylanilines, Aryl Iodides, and CO₂ toward 3,3-Diaryl 2,4-Quinolinediones

Palladium-catalyzed multicomponent reactions (MCRs) between <i>o</i>-alkynylanlines, aryl iodides, and atmospheric pressure of CO₂ are developed, affording a series of 3,3-diaryl 2,4-quinolinediones bearing a newly constructed quaternary carbon center in moderate to excellent yields. The reaction proceeded with a sequential carboxylation, <i>trans</i>-oxopalladation of CC bond by ArPdX species, and reductive elimination procedure leading to benzoxazine-2-ones bearing tetrasubstituted vinyl fragments. Then, rearrangement of benzoxazine-2-ones took place toward 3,3-diaryl 2,4-quinolinediones. This procedure features simultaneous formation of four bonds in one pot