Remote Diastereoselection in the Asymmetric Total Synthesis of Mevinolin

Article abstract of DOI:10.1021/ja00189a037

The asymmetric total synthesis of mevinolin (1a) is described.The key diastereoselective processes used to parlay the lone stereogenic center of asymmetrically produced (S)-pulegone (2a) to mevinolin include orthoester-Claisen rearrangement of 2d to 3a, stereoselective iodolactonization of 3e to 4, Eschenmoser-Claisen rearrangement of 6 to 7a, stereoselective intramolecular ene reaction of 7b to 8, and a highly diastereoselective cyclocondesation of aldehyde 10 with Danishefsky's diene.The cyclocondensation reaction was found to be quite sensitive to the reactionconditions in which the use of TiCl4 produced a 90:10 mixture of 11/12 while MgBr2 gave a 22:78 mixture