Synthesis of P-Substituted 5- and 6-Membered Benzo-Phostams: 2,3-Dihydro-1H-1,2-benzazaphosphole 2-Oxides and 2,3-Tetrahydro-1H-1,2-benzazaphosphinine 2-Oxides

Several approaches were developed for the preparation of phosphorus-substituted 5- and 6-membered benzophostams. Carbodiimide-promoted cyclization of zwitterionic aminophosphinates derived from a nitrobenzene precursor accomplished the cyclization in good yields. Alternatively, a novel copper-catalyzed cross-coupling between a phosphonamide and a bromobenzene precursor produced the heterocycles in moderate to good yields. Three different methods are compared for the synthesis of the P-ethoxy-substituted 5-membered benzophostam.