新型五氟苯铵三氟有机催化剂高效合成14-芳基(烷基)-14H-二苯并[a,j]呫吨类化合物和1,8-二氧代氧杂蒽衍生物(英文)

A simple and facile synthesis of 14-aryl and alkyl-14H-dibenzo[a,j]xanthenes and 1,8-dioxooctahydroxanthene derivatives has been successfully developed by treatment of β-naphthol or dimedone with aldehydes under mild conditions in the presence of a pentafluorophenyl ammonium triflate(PFPAT) organocatalyst.These catalytic condensation reactions represent green chemical processes and the PFPAT organocatalyst is air-stable,cost-effective,easy to handle,and easily removed from the reaction mixtures.     

An approach to the Paal-Knorr pyrroles synthesis catalyzed by Sc(OTf)3 under solvent-free conditions

A facile synthesis of N-substituted pyrroles by the Paal-Knorr condensation has been accomplished using a simple procedure. Among different metal triflates screened, 1 mol % Sc(OTf)₃ efficiently promoted the reaction to give excellent yield (89-98%) under mild reaction conditions. Additionally, Sc(OTf)₃ could be recovered easily after the reactions and reused without evident loss in activity.     

An efficient synthesis of cyclic urethanes from Boc-protected amino acids through a metal triflate-catalyzed intramolecular diazocarbonyl insertion reaction

A simple and efficient synthesis of cyclic urethanes and related oxazinanones 1a-l from diazoketones 3a-l is described. The transformation involves generation of carbenes by activation of diazo groups using metal triflates in intramolecular diazocarbonyl insertion reactions in high overall yields.     

1,5-Benzoheteroazepines through eco-friendly general condensation reactions

Condensation reactions of o-phenylenediamine and 2 equiv of acetone produce biaryl-substituted 1,5-benzodiazepines. The synthetic protocol shows general applicability since similar reaction of o-phenylenediamines, o-aminophenol, and o-aminothiophenol with ketones or chalcones leads to formation of functionalized 1,5-benzoheteroazepines in good to excellent yields. The synthetic protocol fulfills many green-chemical requirements using simple MW-assistance to promote the activation of ketones and the eco-compatible Er(III) triflate as activator of chalcones.     

Reaction products of nitronyl nitroxyl radicals with acids

Study of the structures of compounds generated by the reactions of 4,4,5,5-tetramethyl-2-phenyl-4,5-dihydro-1H-imidazole-1-oxyl 3-oxide with trifluoromethanesulfonic and picric acids demonstrated that these reactions produced salts of disproportionation products of nitronyl nitroxyl.     

Mild and Highly Efficient Protocol for the Synthesis of Benzimidazoles Using Samarium Triflate [Sm(OTf)3]

One-pot synthesis of benzimidazole compounds from ortho-phenylenediamine and a variety of aldehydes was developed under mild reaction conditions. All the reactions were carried out in the presence of samarium triflate (10 mol%) in acetonitrile at room temperature.     

Convenient approach to novel functional substituted and branched poly(silylenemethylenes)

Novel poly(silylenemethylenes) have been prepared by the ring-opening polymerization of 1,3-disilacyclobutanes followed by a protodesilylation reaction with triflic acid. The silicon–aryl bond cleavage could be controlled by using different leaving groups, for instance phenyl- and para-anisyl substituents. The reactions of the triflate derivatives with organomagnesium compounds, LiAlH₄, amines, or alcohols gave functional substituted poly(silylenemethylenes). Hydrosilylation reactions or reductive coupling with potassium–graphite led to organosilicon network–polymers, which may serve as suitable precursors for silicon carbide and Si/C/N-based materials. The structures of the polymers were identified by NMR spectroscopy (²⁹Si, ¹³C, ¹H). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 725–735, 1998     

L-ProT catalyzed highly regioselective N-alkoxyalkylation of purine rings with vinyl ethers

An efficient and regioselective synthesis of N-9 alkoxyalkylated purine nucleoside derivatives was achieved via the N-alkoxyalkylation of purine rings with vinyl ethers catalyzed by L-ProT.The advantages of this protocol include good to excellent yield,mild reaction condition,and simple manipulation.A plausible mechanism for the transformation was given.     

Clay Supported Ammonium Nitrate “Clayan” : A Rapid and Convenient Regeneration of Carbonyls in Dry Media

Regeneration of carbonyls from their oximes, phenylhydrazones and tosylhydrazones derivatives using clay supported ammonium nitrate “clayan” under microwave irridiation is described. The inexpensive reagent and solvent free condition makes the procedure simple and economic.     

Ytterbium triflate catalyzed synthesis of chlorinated lactones

The direct synthesis of chlorolactones from differently substituted alkenoic acids, using either sodium hypochlorite or chloramine T as the source of electrophilic chlorine and ytterbium triflate hydrate as the Lewis acid is described. In both cases the reactions proceeded in good yields affording selectively five- or six-membered chlorolactones.     

Highly Efficient Aminolysis of Epoxides Catalyzed by Reusable Zirconyl Triflate,ZrO(OTf)2

Efficient ring opening of epoxides with aromatic amines catalyzed by ZrO(OTf)₂ is reported, and the corresponding β amino (beta-amino acid) alcohols were obtained in high yields in CH₃CN as solvent. The reactions were carried out at room temperature and in the presence of only 1.25 mol% of ZrO(OTf)₂. This catalyst can be reused several times without loss of its activity.     

Microwave-promoted aminocarbonylation of aryl triflates using Mo(CO)6 as a solid CO source

Palladium-catalyzed carbonylations of aryl triflates with a range of nucleophiles using Mo(CO)₆ as a solid CO source were explored. The reactions proceeded smoothly providing moderate to good yields of the corresponding aryl amides, esters, or acylsulfonamides after only 20 min of microwave irradiation. The acyl transfer reagent 4-dimethylaminopyridine was found to promote some of the more difficult transformations.     

Efficient synthesis of arylsulfamides by reaction of amines with arylsulfamoyl imidazolium triflate

Arylsulfamoyl imidazolium triflates, readily prepared from the corresponding chlorides, react with amines under neutral conditions to form arylsulfamides in high yields. This methodology, which contrasts with the slow and inefficient reactions of amines with arylsulfamoyl chlorides, is applied to the synthesis of arylsulfamide 3a, a bioisotere of muraglitazar.     

Catalytic Activation of Olefins by Metal Triflates and Triflimides: Application to Fragrance Chemistry

Fragrance compounds constitute a wide family of relatively volatile compounds presenting interesting odour properties. Several processes catalysed by metal triflates and triflimides have been recently developed with a view to applications to fragrance chemistry. These reactions, involving the activation of non‐activated olefins, mainly involve inter‐ and intramolecular carbon–carbon, carbon–oxygen and carbon–sulfur bond formation.     

A tandem enol silane formation-Mukaiyama aldol reaction mediated by TMSOTf

A slight excess of silyl trifluoromethanesulfonate mediates a tandem enol silane formation-Mukaiyama aldol reaction in the presence of Hunig’s base. Preformation of the enol silane is unnecessary for efficient reactions, which proceed in 75-97% yield for the addition of aryl methyl ketones and acetate esters to non-enolizable aldehydes. Mechanistic data suggests that free amine is crucial for full conversion.     

Pentafluorophenylammonium triflate as an efficient, environmentally friendly and novel organocatalyst for synthesis of bis-indolyl methane derivatives

A simple, inexpensive, environmentally friendly and efficient route for the synthesis of bis-indolyl methane derivatives by the reaction of indole or N-methyl indole with aldehydes using pentafluorophenylammonium triflate (PFPAT) as a catalyst is described. PFPAT organocatalyst is air-stable, cost-effective, easy to handle, and easily removed from the reaction mixtures.     

Organocatalytic synthesis of amides from nitriles via the Ritter reaction

A simple, inexpensive, environmentally friendly, and efficient route for the synthesis of a wide variety of amides in high yields via the Ritter reaction of alcohols with nitriles has been demonstrated. Pentafluorophenyl ammonium triflate (PFPAT) is used as an organocatalyst and is air-stable, cost-effective, easy to handle, and easily removed from the reaction mixtures.     

AgOTf-catalyzed one-pot reaction of 2-alkynylbenzaldehyde, amine, and sodium borohydride

One-pot reactions of 2-alkynylbenzaldehydes, amines, and sodium borohydride catalyzed by AgOTf under mild conditions provide a facile protocol for the concise synthesis of 1,2-dihydroisoquinoline derivatives.     

A silver(I)-catalyzed reaction of 2-alkynylbenzaldoxime with arylsulfonyl chloride

A silver-catalyzed reaction of 2-alkynylbenzaldoxime with arylsulfonyl chloride proceeds smoothly at room temperature to afford 4-tosyloxyisoquinolines in moderate to good yields. Additionally, the resulting 4-tosyloxyisoquinolines could be further elaborated through palladium-catalyzed coupling reactions leading to diverse isoquinolines.     

Synthesis and functionalization of Poly[5,5′‐(silylene)‐2,2′‐dithienylene]s using silyl triflate intermediates†

Treatment of 5,5′‐dilithio‐2,2′‐dithiophene with (dimethylamino)methylsily bis(triflate)‐ or α, ω‐bis(triflate)‐substituted trisilanes gave poly[5,5′‐(silylene)‐2,2′‐dithienylene]s in high yields. The amino–silyl bond was cleaved selectively by triflic acid, leading to triflate‐substituted derivatives. Conversion of these compounds with nucleophiles gave other functionalized polymers. Platinum‐catalyzed hydrosilylation reactions between silicon–vinyl and silicon–hydrogen derivatives result in polymer networks which may serve as interesting preceramic materials. The structures of the polymers were proven by NMR spectroscopy (²⁹Si, ¹³C, ¹H). Results of thermal gravimetric analysis (TGA), UV spectrometry and conductivity measurements are given. Copyright © 1999 John Wiley & Sons, Ltd.