Stereoselective Synthesis of <i>trans</i>-1,2,4-Trihydrobenzo[<i>d</i>][1,2]azaphosphinine 3‑Oxides from <i>In Situ</i> Formed Phosphenes and Formaldimines

Various trans-1,2,4-trihydrobenzo[d][1,2]azaphosphinine 3-oxides are synthesized highly stereoselectively from in situ generated phosphenes and formaldimines under microwave irradiation. Aryl(diazo)methyl(diaryl)phosphine oxides first undergo the Wolff rearrangement to generate phosphenes. Imines, in situ generated from 1,3,5-triazinanes or paraformaldehyde and primary amines, nucleophilically attack the phosphenes followed by a tandem stereoelectronic effect-controlled intramolecular nucleophilic addition and aromatization to give final trans-1,2,4-trihydrobenzo[d][1,2]azaphosphinine 3-oxides, exhibiting completely different annuloselectivity from linear nonformaldimines.