Synthetic Routes to Allenic Acids and Esters and Their Stereospecific Conversion to Butenolides

The synthesis of allenic acids and esters and their conversion to butenolides has been examined in some detail. Racemic butenolides 10 are efficiently prepared from the esters 8 through treatment with BCl(3) and exposure of the derived acid 9 to catalytic AgNO(3) in acetone. Conversion of the enantioenriched allenylstannane (S)-17 to the acid 18 through lithiation and subsequent carboxylation with CO(2) afforded racemic product. The enantioenriched propargylic mesylates 16 and 22 afforded the allenic esters 19 and 23 with inversion of configuration through treatment with Pd(Ph(3)P)(4), CO, and the appropriate alcohol in THF. These reactions proceeded with ca. 10% or less of racemization. The allenic esters 23 yielded the iodobutenolides 24 by reaction with IBr. Hydrogenolysis to the butenolide 25 was achieved with Pd(PPh(3))(4) and Bu(3)SnH. Alternatively, the allenic acids 27 could be prepared directly from mesylates 22 with Pd(PPh(3))(4) and CO in aqueous THF. Cyclization to the butenolides 25 was achieved, as before, with catalytic AgNO(3).