After synthesising the potassium salt of the phosphaethynolate anion in 2013, Goicoechea et al. began to look into the potential of PCO towards cycloadditions. They found that the anion could react in a [2+2] fashion with a diphenyl ketene to produce the first isolatable example of a four-membered monoanionic phosphorus containing heterocycle. They employed the same method to test other unsaturated substrates such as carbodiimides and found that the likelihood of cyclisation heavily relies on the nature of the substituents on the unsaturated substrate.
Cycloaddition reactions involving the phosphaethynolate anion have also been shown by Grutzmacher and co-workers to be a viable synthetic route to other heterocycles. One simple example is the reaction between the NaPCO and an α-pyrone. This reaction yields the sodium phosphinin-2-olate salt which is stable to both air and moisture.