Azulenesulfonium Salts: Accessible,Stable, and Versatile Reagents for Cross‐Coupling

Azulenesulfonium salts may be readily prepared from the corresponding azulenes by an S_EAr reaction. These azulene sulfonium salts are bench‐stable species that may be employed as pseudohalides for cross‐coupling. Specifically, their application in Suzuki–Miyaura reactions has been demonstrated with a diverse selection of coupling partners. These azulenesulfonium salts possess significant advantages in comparison with the corresponding azulenyl halides, which are known to be unstable and difficult to prepare in pure form.     

Azulenesulfonium Salts: Accessible,Stable, and Versatile Reagents for Cross‐Coupling

Azulenesulfonium salts may be readily prepared from the corresponding azulenes by an S_EAr reaction. These azulene sulfonium salts are bench‐stable species that may be employed as pseudohalides for cross‐coupling. Specifically, their application in Suzuki–Miyaura reactions has been demonstrated with a diverse selection of coupling partners. These azulenesulfonium salts possess significant advantages in comparison with the corresponding azulenyl halides, which are known to be unstable and difficult to prepare in pure form.     

Truce-Smiles Rearrangement of Diaryliodonium Salts in Ionic Liquids

The Truce-Smiles rearrangement is an intramolecular S_NAr reaction, enabling the formation of a new arene carbon-carbon bond with sufficiently strong carbon-centered nucleophile. Reported here are ortho-tosylmethylene functionalized diaryliodonium salts, which can undergo an unprecedented Truce-Smiles rearrangement in ionic liquids, resulting in sulfonyl-substituted ortho-iodo diarylmethanes as a powerful class of building blocks in chemical synthesis. The protocol features aryliodo moiety as a hyper nucleofuge, facilitating the formation of Meisenheimer complex within the migratory system.     

Stevens Rearrangement of Anilinium Salts By the Action Sodium Carbonate Hexahydrate

Anilinium salts containing an allyl-like group together with various functionally substituted receiving groups undergo Stevens rearrangement by the action of sodium carbonate hexahydrate in the absence of a solvent. As a result, both N-methylaniline derivatives and nucleophilic substitution products are formed.     

异噁唑啉盐的合成及其应用

作为一类重要的有机合成中间体,异噁唑啉盐广泛地应用于具有生物活性化合物的制备.对异噁唑啉盐的结构、制备方法,及其作为多功能合成中间体,在N-甲基异噁唑烷、N-甲基氨基醇、N-甲基氨基多醇、α-氨基酸和β-氨基酸等重要化合物合成中的应用作了较详尽阐述,同时简单地介绍了新型N-取代异噁唑啉盐的合成及其应用.在对这些研究现状进行分析的基础上,对该研究领域下一步的发展方向进行了展望.     

Synthesis and Photoarylotropic Rearrangement of 10-Phenoxynaphthacenokeramidonine

Russian Journal of Organic Chemistry -     

Synthesis and Rearrangement Reactions of C-Alkylidene Carbohydrates

Direct: olefinations on one hand in comparison to eliminations of aldols cf various uloses on the other each proved to be specific as to the sice of unsaturation in the branched-chain products, found to be interconvertible with one exception under a variety of conditions. Although shown to be generally equivalent to its Witcig-counterpart:, the Peterson reagent employed is liable to cause eliminations in the initial olefin. One of the branched-chain products appears to be of unusual molecular rigidity as evidenced by a large 5J coupling.     

9-亚胺二苯并型环状碘鎓盐的合成

二苯并型环状碘鎓盐(结构通式如1)是一类人工合成的化合物,近30年的研究表明,某些二苯并型环状碘鎓盐具有抑菌、降血压,抗辐射及抗心律失常^[1-4]等生理活性.     

Synthesis of Norcantharidin Complex Salts

A new series of norcantharidin salt derivatives was designed and synthesized in good yield. The compounds structures were characterized by ¹H‐NMR, ¹³C‐NMR, and IR spectra. These norcantharidin salts 5 exhibit good antitumor activity against both liver cancer and colon cancer cell lines in vitro, which seems to direct a right trend for the modification on cantharidin structure.     

Aromatic Aza-Claisen Rearrangement of Arylpropargylammonium Salts Generated in situ from Arynes and Tertiary Propargylamines

The charge-accelerated aza-Claisen rearrangement of ammonium salts serves as a key step in the construction of complex nitrogen-containing molecules. However, much less attention has been paid to the aromatic aza-Claisen rearrangement than to the aliphatic one. Herein, we report an unprecedented aromatic aza-Claisen rearrangement of arylpropargylammonium salts, generated in situ from arynes and tertiary propargylamines, delivering structurally diverse 2-propargylanilines in moderate to good yields with high regioselectivity. This rearrangement proceeds in the absence of strong bases or transition metals, is compatible with moisture and air, tolerates a wide variety of functional groups, and is amenable to forming 11- to 13-membered heterocycles with a triple bond. The 2-propargylaniline products were treated with aluminum chloride in ethanol to afford multisubstituted indoles in moderate to excellent yields. Finally, a series of deuterium-labeling experiments was performed to elucidate the reaction mechanism.     

Synthesis of Aminophosphonium Salts and Their Transformation

Abstract

Aminophosponium salts were obtained by two different methods: (1) catalytic phosphorilation of halogen derivatives containing Csp2-Hlg bonds; (2) uncatalytic phosphorilation of bromoacetal. Reactions mechanisms are discussed.     

Synthesis and Structures of Potassium Bisdithiocarbamate Salts

Two structurally related dipotassium bisdithiocarbamate salts: K₂[(S₂CNRCH₂)₂](EtOH)₂; R = Me, i‐Pr, were synthesised from the corresponding diamines. X‐ray structure determinations were performed on single crystals grown from ethanolic solutions. The different alkyl substituents have a profound affect upon the solid‐state structures, with the methyl derivative possessing a complex a 3‐D network and the isopropyl derivative a 2‐D lamellar structure.     

Synthesis and Reactivity of Unsaturated Bisphosphonium Salts

Abstract

The synthesis of 1, 2 vinylene bisphosphonium salts 1 has now been enlarged to the vinylogous 1, 4-butadienylene bisphosphonium salts 2. The salts 2, a new class of unsaturated disalts, have also been prepared through a two-step isomerisation of acetylenic salts. New aspects of the reactivity of salts 1 and the comparative study of salts 2 (selective cleavage reactions of P-C bonds and reactions with nucleophiles having a mobile hydrogen) are described. This reactivity allows the preparation of new series of phosphonium salts substituted by heteroatomic groups.     

Synthesis of Helical and Planar Extended-Phenanthridinium Salts

The investigation of new synthetic routes towards positively charged N-heterocycles is of high importance for the further development of medicinal chemistry, functional materials, catalysis and other areas of application. For accessing acridinium dyes, we previously reported an approach based on an aryne-imine-aryne coupling followed by the subsequent oxidation of the acridane intermediates. Herein, we now present an unusual reaction outcome when phenanthryne is used as aryne component. Under optimized conditions, this two-step synthetic methodology led to the formation of a helical tetrabenzophenanthridinium derivative. Furthermore, the susceptibility of this product to photoinduced cyclodehydrogenation was observed, providing a highly fluorescent planar polycyclic aromatic hydrocarbon with a positively charged nitrogen. The photophysical and electrochemical properties of the mesityl-phenyltetrabenzophenanthridinium tetrafluoroborate were also determined.     

水溶性有机膦盐的合成与表征

高产率地合成了三苯基磷间磺酸铵[MPA,(C6H5)2P(m-C6H4SO3^-NH4 )]和两种季膦盐[MPAE,(C6H5)2P^ (m-C6H4SO3^-)CH2CO2Et],[TPEI,(Ph3CH2CO2Et)I^-],初步研究了其理化性质。     

Stevens Rearrangement of Ammonium Salts Containing 3-Methyl-3-ethoxycarbonylbutanon-2-yl Group

Ammonium salts containing alongside 3-methyl-3-ethoxycarbonylbutanon-2-yl also 2-alkenyl or benzyl groups under the treatment with Na₂CO₃·10H₂O afford products resulting from Stevens rearrangement. In the mentioned salts the ketoester group on treatment with sodium ethylate suspension in ether or benzene suffers partial or total acid cleavage, and then the Stevens 3,2-rearrangement takes place.