General Strategy for Stereoselective Synthesis of 1-Substituted Exo,Endo-2,6-Diaryl-3,7-dioxabicyclo[3.3.0]octanes: Total Synthesis of (±)-Gmelinol

[reaction: see text] A general strategy for stereoselective synthesis of 1-substituted exo,endo-2,6-diaryl-3,7-dioxabicyclo[3.3.0]octanes including (+/-)-gmelinol from (2,3-trans)-(4,5-cis)-alpha-aroylparaconic esters, which are readily obtained from the reaction of vicinal dianions derived from alpha-aroylsuccinic esters with aromatic aldehydes, is described. The synthetic sequence involves alpha-methylation or alpha-hydroxylation, reduction, bislactonization, and reduction followed by furofuran formation.