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Synthesis of 1,4-dihydrophosphinoline 1-oxides by acid-promoted cyclization of 1-(diphenylphosphoryl)allenes†
Alexander S. Bogachenkov,Albina V. Dogadina,Irina A. Boyarskaya,Vadim P. Boyarskiy
Organic & Biomolecular Chemistry Pub Date : 11/27/2015 00:00:00 , DOI:10.1039/C5OB02143J
Abstract

1-(Diphenylphosphoryl)alka-1,2-dienes (phosphonoallenes) in Brønsted (super)acids (TfOH, FSO3H, H2SO4) gave the corresponding 1,2-oxaphosphol-3-enium ions, that were studied by means of NMR and DFT calculations. Upon hydrolysis of reaction solution, these cations afforded 3-hydroxyalk-2-en-1-yl-diphenylphosphine oxides (phosphonoallyl alcohols). But in (super)acids the cations were slowly transformed into O-protonated forms of 1-phenyl-1,4-dihydrophosphinoline 1-oxides, which were monitored by NMR. The latter phosphaheterocycles can be directly obtained from phosphonoallenes under the action of Lewis acid AlCl3.

Graphical abstract: Synthesis of 1,4-dihydrophosphinoline 1-oxides by acid-promoted cyclization of 1-(diphenylphosphoryl)allenes
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