Novel 1-phosphonyl radicals derived from 1-mono and 1,1-di-heterosubstituted 2-oxoalkylphosphonates as useful phosphotoorganic intermediates in organic synthesis

Article abstract of DOI:10.1016/S0040-4020(96)01122-2

Novel 1-phosphonyl radicals 17 were obtained from 1-mono(Y=H X=Cl, Br, SMe) and 1.1-di (Y=X=Cl) hetero substituted 2-oxoalkylphosphonates 16 under the reductive conditions (n-Bu₃SnH/AIBN) and utilized in the reactions with alkenes for the free-radical synthesis of highly functionalized phosphonates 19 and 20. The utility of the new approach has been demonstrated by the synthesis of methylenomycin B 13, a cyclopentanoid antibiotic, using the phosphonate 19d as well as by the synthesis of 4-diethoxyphosphoryl-2,3-dihydrofuran 22 and 2-diethoxyphosphoryloxy-heptan-5-one 23.