Organophosphorus Compounds, 112. Lewis Acid Mediated Spirocyclotrimerization of Kinetically Stabilized Phosphaalkynes – Key Step for the Selective Generation and Trapping of Triphospha Dewar Benzenes

Abstract

AbstractIn the presence of Lewis acidic derivatives of group 13 elements, phosphaalkynes 7 undergo spirocyclotrimerization with incorporation of the corresponding Lewis acids to form 10a–f. Scope and limitations of this novel cyclooligomerization process are examined. Starting from the spirocyclotrimer 10a reaction with the Lewis base dimethyl sulfoxide, we have in hand for the first time a method for the selective generation of two isomeric triphospha Dewar benzene derivatives (18, 19). Both can be trapped efficiently by further reaction with the phosphaalkyne to furnish the two novel phosphaalkyne cyclotetramers 20 and 21, both still possessing a phosphorus–carbon double bond. In the case of 21, further functionalization of the phosphaalkene unit is possible by [3 + 2] cycloaddition with a nitrile oxide (→ 23).