A hitherto unknown triphosphatricyclo[3.2.1.02,7]oct-3-ene was obtained in high yield by a total of four consecutive pericyclic reactions from di-2-pyrone and excess TMS-C[triple bond, length as m-dash]P. DFT calculations gave insight into the reaction mechanism. The chiral phosphorus cage readily forms coordination compounds with Au(i) and Cu(i).
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