The synthesis and some reactions of N-methylnitrilium trifluoromethanesulphonate salts

Abstract

N-Methylnitrilium trifluoromethanesulphonate nitrile and @-unsaturated nitriles is slow, and is usually (triflate) salts, prepared from nitriles and methyl triflate, accompanied by s-triazine formation. This nitrile cyclohave been shown to be useful reagents for the synthesis of trimerisation reaction is probably catalysed by a trace of aromatic ketimines and ketones, amidinium, imidate, and triflic acid which is difficult to remove completely from the thioimidate salts, benzimidazoles, benzoxazoles, benzo-methyl triflate, prepared from triflic acid and dimethyl thiazoles, quinazolinones, and 1,2,4-triazolinium salts.su1phate.l p 2 Triazine formation with benzonitrile and acrylonitrile can be reduced to insignificant levels by 1

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

“…[1, 6,8,9] We were keen on developing a scalable and efficient synthesis of a range of nitrilium ions and exploring their use in the preparation of 1,3-P,N ligands. [10] The archetypical P,N ligand 2-pyridyldiphenylphosphane (B) has found widespread application in coordination chemistry and catalysis [10c, 11] in spite of its structurally limited N-donor site.…”

ROTf-induced annulation of heteroatom reagents and unsaturated substrates leading to cyclic compounds

“…Nitriles as unsaturated heteroatom reagents could react with ROTf to form N -alkylated nitriliums, which were well investigated by Booth et al [31] in 1980. However, electrophilicity of N -alkylated nitriliums has rarely been used in further reactions until recently.…”

“…As useful and versatile precursors in a variety of organic transformations, many methods have been developed to prepare ROTf, such as the reaction of orthoformates and triflic anhydrides under solvent-free condition [19][20][21][22][23][24][25][26]. The intrinsic electrophilicity of ROTf is often used as alkylation reagents for diverse substrates containing heteroatoms such as P [27], O [28], N [29][30][31], S [32,33], Te [34], Ge [35], Bi [36], Si [37] and Se [38,39], which straightforwardly affords the corresponding alkylated products with aid of base or stable triflates irreversibly that even could be applied as ionic liquids [40,41]. Moreover, the resulting triflates could be further transformed into other products by substitution [30,[42][43][44] (scheme 1a).…”

“…Moreover, the resulting triflates could be further transformed into other products by substitution [30,[42][43][44] (scheme 1a). On the other hand, unsaturated heteroatom-containing reagents, such as nitriles, aldehydes, isocyanates and isothiocyanates, could be captured by ROTf to generate electrophiles bearing carbon cations [29,31,45,46], which could be subsequently reacted with appropriate unsaturated substrates to produce cyclic compounds by tandem electrophilic reactions/cyclization (scheme 1b); although HOTf or HNTf 2 as a catalyst or promoter also demonstrated excellent electrophilic cyclization involving alkynes or alkenes. However, preparing highly functionalized heterocycles is still difficult.…”

One-pot synthesis of benzoxazoles via the metal-free ortho-C–H functionalization of phenols with nitroalkanes

“…4 Development of polybenzobisoxazoles led to the discovery of a new generation of organic polymers for electronics and novel high tensile materials. 6 The most straightforward approaches to benzoxazoles involve various cyclocondensations between o-aminophenols and different carbonyl derivatives: aldehydes, 7 imines, 8 carboxylic acids, 9 acyl halides, 10 esters, 11 orthoesters, 12 N-alkylnitrilium salts, 13 isocyanides, 14 or carbon monoxide. 6 The most straightforward approaches to benzoxazoles involve various cyclocondensations between o-aminophenols and different carbonyl derivatives: aldehydes, 7 imines, 8 carboxylic acids, 9 acyl halides, 10 esters, 11 orthoesters, 12 N-alkylnitrilium salts, 13 isocyanides, 14 or carbon monoxide.…”