Regiochemistry of Vinyl Phosphate/β-Keto Phosphonate Rearrangements in Functionalized Cyclohexanones and Cyclohexenones

Article abstract of DOI:10.1021/jo00027a055

Diethyl vinyl phosphates derived from simple alkyl-substituted cyclohexanones and cyclohexenones are known to rearrange to β-keto phosphonates upon treatment with excess LDA.To establish the effect of oxygen-containing functional groups on this transformation, vinyl phosphates containing remote carbonyl groups or acetals have been studied.The rearrangement fails in the presence of unprotected carbonyl groups but proceeds in the presence of acetals.To establish the regiochemistry of this rearrangement in fused-ring systems, representative decalins were studied.Through use of various ketones and enones, the 2- and 4-phosphono 3-keto compounds have been prepared in both cis- and trans-fused decalin series.