Oxophosphonium-Alkyne Cycloaddition Reactions: Reversible Formation of 1,2-Oxaphosphetes and Six-membered Phosphorus Heterocycles.

While the metathesis reaction between alkynes and carbonyl compounds is an important tool in organic synthesis, the reactivity of alkynes with isoelectronic main-group RE═O compounds is unexplored. Herein, we show that oxophosphonium ions, which are the isoelectronic phosphorus congeners to carbonyl compounds, undergo [2 + 2] cycloaddition reactions with different alkynes to generate 1,2-oxaphosphete ions, which were isolated and structurally characterized. The strained phosphorus-oxygen heterocycles open to the corresponding heterodiene structure at elevated temperature, which was used to generate six-membered phosphorus heterocycles via hetero Diels-Alder reactions. Insights into the influence of the substituents at the phosphorus center on the energy profile of the oxygen atom transfer reaction were obtained by quantum-chemical calculations.