ChemInform Abstract: BROMOMETHYL ISOCYANATE AND ITS PHOSPHORYLATED DERIVATIVES

Shokol, V. A.; Silina, E. B.; Kozhushko, B. N.; Golik, G. A.

doi:10.1002/chin.197934280

Cited by 1 publication

(1 citation statement)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reactions were carried out in methanol by bubbling HCl gas through the substrate solution or by treating it with aqueous HBr or HI [ 29 ]. 1-( N -alkoxycarbonyl)methyltriphenylphosphonium chlorides or bromides ( 4a , R 1 = OR, X = Cl or Br) were obtained by Kozhushko et al in the reaction of triphenylphosphine with chloromethylisocyanate or bromomethylisocyanate and further hydrolysis of the isocyanate group ( Scheme 3 , Method C) [ 30 , 31 ]. In analogous reactions, the corresponding triphenylphosphonium iodides ( 4a , R 1 = OR, X = I) were also obtained by adding methyl iodide in the first step of the synthesis [ 32 ].…”

Section: 1-aminoalkyltriarylphosphonium Derivativesmentioning

confidence: 99%

1-Aminoalkylphosphonium Derivatives: Smart Synthetic Equivalents of N-Acyliminium-Type Cations, and Maybe Something More: A Review

et al. 2022

View full text Add to dashboard Cite

N-acyliminium-type cations are examples of highly reactive intermediates that are willingly used in organic synthesis in intra- or intermolecular α-amidoalkylation reactions. They are usually generated in situ from their corresponding precursors in the presence of acidic catalysts (Brønsted or Lewis acids). In this context, 1-aminoalkyltriarylphosphonium derivatives deserve particular attention. The positively charged phosphonium moiety located in the immediate vicinity of the N-acyl group significantly facilitates Cα-P+ bond breaking, even without the use of catalyst. Moreover, minor structural modifications of 1-aminoalkyltriarylphosphonium derivatives make it possible to modulate their reactivity in a simple way. Therefore, these types of compounds can be considered as smart synthetic equivalents of N-acyliminium-type cations. This review intends to familiarize a wide audience with the unique properties of 1-aminoalkyltriarylphosphonium derivatives and encourage their wider use in organic synthesis. Hence, the most important methods for the preparation of 1-aminoalkyltriarylphosphonium salts, as well as the area of their potential synthetic utilization, are demonstrated. In particular, the structure–reactivity correlations for the phosphonium salts are discussed. It was shown that 1-aminoalkyltriarylphosphonium salts are not only an interesting alternative to other α-amidoalkylating agents but also can be used in such important transformations as the Wittig reaction or heterocyclizations. Finally, the prospects and limitations of their further applications in synthesis and medicinal chemistry were considered.

show abstract