Mechanisms of stereomutation and thermolysis of spiro-1,2-oxaphosphetanes: New insights into the second step of the wittig reaction

Article abstract of DOI:10.1021/ja307330c

The experimentally observed stereomutation of spiro-1,2-oxaphosphetanes is shown by DFT calculations to proceed through successive M_B2 or M _B4 and M_B3 mechanisms involving two, four, and three Berry pseudorotations at phosphorus, respectively. Oxaphosphetane decomposition takes place in a single step via a polar transition state. The calculated activation parameters for this reaction are in good agreement with those determined experimentally.