Tricoordinated phosphorus‐containing macrocycles: New synthetic strategies

Phosphorus dialdehydes RP (OC6H4CHO)2 (R = Ph, Me2N) react with phosphodihydrazides PhP(Y)‐[N(CH3)NH2]2 (Y = S, O) to give macrocycles 6a–c arising from [2 + 2] cyclocondensation reactions. Treatment of phosphodihydrazone PhP(S) [OC6H4CHN–N(Me)H]2 7 with phenyldichlorophosphine affords macrocycle 8 possessing tri and tetracoordinated phosphorus atoms. Clean desulfurization of thiophosphorus macrocycles 9 and 12 gives rise selectively to new tricoordinated phosphorus containing macrocycles 11 and 13.