Synthesis of 1-substituted 2,9,10-trioxatricyclo[4.3.1.03,8]decanes

A series of 1-alkyl- and 1-alkenyl-2,9,10-trioxatricyclo[4.3.1.03,8]decanes, models for the core orthoester structural moiety of resiniferatoxin and synaptolepis factors, was prepared by a transetherification reaction of (±)-all-cis-cyclohexane-1,2,4-triol and trimethyl orthocarboxylates. The synthesis of the starting trimethyl orthocarboxylates is also given in detail.