Direct Condensation of Sulfonamide and Formamide: NaI-Catalyzed Synthesis of <i>N</i>-Sulfonyl Formamidine Using TBHP as Oxidant

A new N-sulfonyl formamidine synthesis was developed via NaI-catalyzed direct condensation of sulfonamide and formamide. The green methodology is featured by high atom economy, easily available starting materials, the lack of need for a transition-metal catalyst, no requirement of hazardous reagent, operational simplicity, and good tolerance with diverse functional groups. Mechanistic studies suggest that the protocol proceeds based upon in situ generated TsN·NaI

Ortho Arylation of Acetanilides via Pd(II)-Catalyzed C−H Functionalization

A remarkable transformation to realize ortho arylation of acetanilides via Pd(II)-catalyzed C−H functionalization with trialkoxyarylsinaes was demonstrated

In Situ Generation of Nitrilimines from Aryldiazonium Salts and Diazo Esters: Synthesis of Fully Substituted Pyrazoles under Room Temperature

A novel one-pot synthesis for fully substituted pyrazoles has been well developed via the in situ generation of nitrilimines from aryldiazonium salts and diazo esters and a subsequent cycloaddition with 1,3-dicarbonyl compounds. High yields, mild conditions, wide substrate scope, and operational simplicity are the significant advantages of this methodology

Iodide-Catalyzed Synthesis of <i>N</i>‑Nitrosamines via C–N Cleavage of Nitromethane

An iodide-catalyzed process to synthesize <i>N</i>-nitrosamines has been developed using TBHP as the oxidant. The mild catalytic system succeeded in cleaving the carbon–nitrogen bond in nitromethane. This methodology uses commercially available, inexpensive catalysts and oxidants and has a wide substrate scope and operational simplicity

Interception of Secondary Amide Ylide with Sulfonamides: Catalyst-Controlled Synthesis of <i>N</i>‑Sulfonylamidine Derivatives

A novel, secondary amide activation strategy has been developed through the in situ generation of ylides from amides and diazoacetates. Under the developed reaction conditions, Mn-catalyzed ylide formation and interception reaction by sulfonamide delivered a variety of <i>N</i>-sulfonylamidines. Notably, when highly active Zn­(OTf)₂ was used as the catalyst, further N–H insertion products were obtained. In contrast with traditional methods, our amide activation strategy is distinguished by accessible starting material, inexpensive catalyst, and broad substrate scope

Indirect <i>ortho</i> Functionalization of Substituted Toluenes through <i>ortho</i> Olefination of <i>N</i>,<i>N</i>-Dimethylbenzylamines Tuned by the Acidity of Reaction Conditions

Highly regioselective olefination of substituted N,N-dimethylbenzylamines was developed by tuning the acidity of reaction conditions based on analysis of their features. The ortho-functionalized N,N-dimethylbenzylamines were further transformed into 3-(2‘-tolyl)propanoic acid and its derivatives under mild conditions. These two transformations could be combined into one pot, and 3-(2‘-tolyl)propanoic acid and its derivatives were obtained in moderate to good yields. Mechanistic studies indicated that electrophilic attack on the phenyl ring by the Pd(II) ion assisted by the N,N-dimethylaminomethyl group was a key step during this catalytic transformation, which was controlled by the acidity of the reaction conditions

Synthesis of a Bulky and Electron-Rich Derivative of SEGPhos and Its Application in Ru-Catalyzed Enantioselective Hydrogenation of β-Ketoesters

The synthesis and resolution of a bulky and electron-rich derivative of SEGPhos and its application in Ru-catalyzed asymmetric hydrogenation reaction of β-ketoesters are reported. Up to 99.5% ee was achieved. Under solvent-free reaction conditions, acetoacetates could be reduced with good enantioselectivity and high efficiency; a TON of 20 000 was obtained within 3.5 h. The results obtained were comparable to those when SEGPhos was applied

Radical–Polar Crossover Reactions: Oxidative Coupling of 1,3-Dioxolanes with Electron-Deficient Alkenes and Vinylarenes Based on a Radical Addition and Kornblum–DeLaMare Rearrangement

A new radical-polar crossover reaction has been developed involving the combination of a tandem radical reaction and Kornblum–DeLaMare rearrangement in a one-pot process. This simple methodology allows for the construction of polyfunctionalized carbonyl compounds via the oxidative coupling of 1,3-dioxolanes with electron-deficient alkenes and vinylarenes in the presence of Co­(salen) and TBHP under mild conditions. This reaction also exhibited high functional group tolerance, wide substrate scope, and operational simplicity

A New Strategy for the Construction of α‑Amino Acid Esters via Decarboxylation

A new α-amino acid esters formation reaction has been developed via decarboxylation. The methodology is distinguished by its practical novelty in terms of the readily accessible starting materials, environmentally benign reaction conditions and waste streams, and wide substrate scope

Metal-Free Coupling of 2‑Vinylphenols and Carboxylic Acids: An Access to 3‑Acyloxy-2,3-dihydrobenzofurans

A new coupling reaction between 2-vinylphenols and carboxylic acids was developed to synthesize 3-acyloxy-2,3-dihydrobenzofurans using Bu₄NI as a catalyst and <i>t</i>-BuOOH as an oxidant. This simple and practical methodology is notable due to the ability to complete it under metal-free conditions, with easily available precursors, resulting in a product with high atom economy and high functional group tolerance. Upon the basis of experimental observations and literature, a plausible mechanism is proposed