Аннотация к разделу: Design of novel materials with cutting-edge functions is a highly attractive task for modern chemistry. For such a purpose, reliable and atom-economic scheme of structure modification in the late-steps of synthesis is desired.
: Intramolecular 1,n-HAT-processes (n=5,6,7) were studied by means of DFT calculations. Key factors, governing the processes outcome, are explored and quantitatively characterized. As a result, an economic methodology, which is consistent with recent experimental results, for the description/prediction of the HAT-involved reactions pathway is described.
The review observes the published literature data concerning preparative reactions for the synthesis of 1-oxa-2-phosphol-3-enium salts and highlights the experimental procedures and their analytical NMR, IR, melting points data. The salts were prepared by the reaction of phosphorus-containing allenes with protic acids, Hal2, and R-Hal. The stability and reactivity of the salts discussed with the support of DFT-calculations. The review covers 64 references.
The review observes the published literature data concerning preparative procedures and reactivity of 1-oxa-2-phosphol-3-enium salts as a part of useful 3-step method for ketone derivatization (ketone(aldehyde)→propargylic alcohol→P-bearing allene→P-heterocycle via 1-oxa-2-phosphol-3-enium intermediate). The salts were prepared by the reaction of phosphorus-containing allenes with protic acids, Hal2, and X-Hal. The stability and fruitful reactions of the salts discussed with the support of DFT-calculations. Keywords: phosphorus • heterocycles • DFT • allenes • 1-oxa-2-phosphol-3-enium