Intramolecular Homolytic Substitution of Sulfinates and Sulfinamides

A general and efficient method for the synthesis of cyclic sulfinates and sulfinamides based on intramolecular homolytic substitution (S_Hi) at the sulfur atom by aryl or alkyl radicals is described. Both alkyl and benzofused compounds can be accessed directly from easily prepared acyclic precursors. Enantiomerically enriched sulfur‐based heterocycles were formed through an S_Hi process with inversion of configuration at the sulfur atom. Cyclization of prochiral radicals proceeded with varying stereochemical outcomes, depending on the size of the incoming radical. 2‐Pyridyl and 2‐quinolyl radicals led to biaryl compounds, which result from attack onto the ortho position of the arylsulfinate rather than a thiophilic substitution.     

2-Pyridylsulfinamides as effective catalysts in the asymmetric alkylation of aldehydes with diethylzinc

Chiral 2-pyridylsulfinamides were shown to be effective catalysts in the alkylation of aryl and alkyl aldehydes with diethylzinc providing the corresponding alcohols in excellent enantioselectivity. Sulfinamide catalysts possessing solitary chirality at the sulfur center produced the product phenethyl alcohol in good enantioselectivity. Diastereomeric sulfinamides possessing chirality at the carbon-bearing nitrogen and at the sulfur of the sulfinamide increased the enantioselectivity of the product alcohols up to >99%. However, there is no effect of the match-mismatch pair of sulfinamide diastereomers on the outcome of the chiral induction of the product phenethyl alcohols. It was conclusively proved that chirality at the sulfur center is mandatory for obtaining good enantioselectivity in the reaction.     

Access to Highly Functionalized Sulfonated Cyclopentanes by Acid‐Promoted Rauhut–Currier Reaction with Sulfinamides

An unexpected acid‐mediated cascade reaction induced by conjugate addition of sulfinamides to dienediones has been developed. This highly efficient Rauhut–Currier reaction enables the rapid, high‐yielding construction of sulfonated cyclopentanes with three contiguous stereogenic centers in a single operation starting from simple sulfinamides. This process constitutes the first example of sulfinamide‐promoted cycloisomerization.     

S—H键和N—H键交叉偶联放氢制备亚磺酰胺

利用交叉偶联放氢的方法, 实现了电化学一体池中苯硫酚类化合物与胺类化合物间N—S键的构筑, 高效地制备了一系列亚磺酰胺化合物. 实验结果证实, 该反应通过自由基路径生成的次磺酰胺, 以反应溶剂中微量的水为氧源, 进一步电催化氧化得到亚磺酰胺. 四正丁基碘化铵在反应中可起到电解质和中间体的双重作用.     

Fast and Efficient Synthesis of Sulfinamides by the Oxidation of Sulfenamides Using Potassium Fluoride and m-Chloroperoxybenzoic Acid

A procedure for the synthesis of N-alkyl-, N-cycloalkyl-, N,N-dialkyl-, and N-arylarenesulfinamides from the corresponding sulfenamides using KF/m–chloroperoxybenzoic acid (CPBA) in CH₃CN-H₂O is described. High efficiency (fast reactions, ease of manipulation, and good yields) and absence of overoxidation are the major advantageous features of this protocol.     

Efficient Synthesis of Cyclic Sulfoximines from N-Propargylsulfinamides through Sulfur–Carbon Bond Formation

Cyclic sulfoximines were readily synthesized by the cyclization of N-propargylsulfinamides without using expensive and toxic metal catalysts. This cyclization proceeded without loss of optical purity of chiral sulfinamides through the unusual sulfur–carbon bond formation promoted by an inexpensive inorganic base. This stereospecific cyclization offers a general approach to the asymmetric synthesis of chiral cyclic sulfoximines as an emerging heterocycle in medicinal chemistry.     

Metal‐Free Cross‐Coupling of Arylboronic Acids and Derivatives with DAST‐Type Reagents for Direct Access to Diverse Aromatic Sulfinamides and Sulfonamides

We have developed a simple and convenient method for the cross‐coupling of arylboronic acids and their derivatives with DAST‐type reagents under mild and metal‐free conditions to directly afford sulfinamides in moderate to good yields. Moreover, sulfonamides were obtained after a simple oxidation reaction. The reaction mechanism was investigated by ¹⁸O‐labeling experiments, and the synthetic utility was demonstrated by the sulfoxidation of natural products.