Abstract: | In our laboratory, we have been dealing with the synthesis and utilization of P‐heterocycles for almost two decades. In this paper, our recent results are summarised. In the first part, the synthesis and properties of phospholes with sterically demanding substituent on the phosphorus atom and the fragmentation‐related properties of phosphole oxide‐related 7‐phosphanorbornenes are discussed. Then, new families of 6‐membered P‐heterocycles are introduced available by a ring enlargement method and subsequent modifications. In the next part, I show how bridged P‐heterocycles were prepared and how they were utilised in fragmentation‐related phosphorylations. Finally a novel reaction providing heterocyclic phosphoranes/ylides is discussed. |