Diastereoselective Ring-Closing Metathesis: Synthesis of P-Stereogenic Phosphinates from Prochiral Phosphinic Acid Derivatives

The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties
followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for
the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and
an endocyclic double bond. An investigation into the factors influencing the diastereochemical
outcome of the ring-closing metathesis is also presented, revealing that the geometry of the double
bonds conjugated to phosphorus is important and that 1,3-stereoinduction is superior to 1,4-stereoinduction for these reactions.