Arbuzov-type reaction of acylphosphonites and N-alkoxycarbonylimine cations generated in situ with trifluoroacetic anhydride

Synthesis and Modifications of Phosphinic Dipeptide Analogues

“…As mentioned, the precise role of active carboxyl compounds (in the majority of cases, AcCl) as a driving force for the condensation remained incompletely clear. Recently, this aspect has been studied in detail by Dmitriev and Ragulin [ 64 , 65 , 66 ]. Although acetyl chloride was proven to give the highest yield (approximately 70% yield in the reaction of benzaldehyde, an alkyl carbamate and an alkyl acrylate or methacrylate-derived phosphorus component), other systems were almost equally efficient.…”

“…Indeed, pre-synthesized biscarbamates reacted with phosphorous species 44 to the same extent as both substrates separately under analogous conditions [ 66 ]. To this end, an Arbuzov-type reaction was postulated as an amidoalkylation mechanism responsible for the novel P-C bond formation in 47 ( Scheme 13 ).…”

Formation of phosphorus-carbon bond in the course of amidoalkylation of hydrophosphorylic compounds

“…We have earlier developed an efficient procedure to perform reaction of hydrophosphoryl compounds with aldehydes and alkyl carbamates in acetic anhydride upon cooling, and have proposed the mechanism of this multi-stage reaction [1][2][3][4]. According to the proposed mechanism, the formation of phosphorus-carbon bond is as a result of the Arbuzov reaction via nucleophilic attack of the trivalent phosphorus atom of acetyloxy derivative I at positively charged carbon atom of iminium cation II [1,2], the reactants being generated in situ under the reaction conditions from hydrophosphorylic compound III and N,N'-alkylidenebis(carbamate) IV, respectively [1,2].…”

“…According to the proposed mechanism, the formation of phosphorus-carbon bond is as a result of the Arbuzov reaction via nucleophilic attack of the trivalent phosphorus atom of acetyloxy derivative I at positively charged carbon atom of iminium cation II [1,2], the reactants being generated in situ under the reaction conditions from hydrophosphorylic compound III and N,N'-alkylidenebis(carbamate) IV, respectively [1,2]. Biscarbamates have been identified as stable (isolated from the reaction medium) intermediates formed from the reacting aldehydes and alkyl carbamates [1][2][3][4] (Scheme 1).…”

“…We suggested that transformation of biscarbamate IV into the iminium cation II might occur in the presence of a solid superacid via protonation of nitrogen or oxygen atom (C=O) of amide fragment of biscarbamate with Brønsted sites of the catalyst in an inert solvent followed by evolution of the carbamate [1][2][3][4]. The so…”