An Approach to the 9‑Oxo-10-oxabicyclo[5.3.0]dec-2-ene Core of the Guaianolide and Pseudoguaianolide Sesquiterpenes via a Domino Electrocyclic Ring-Opening/Carboxylic Acid Trapping of a <i>gem</i>-Dibromocyclopropane

A domino silver­(I)-promoted electrocyclic 2π-disrotatory electrocyclic ring-opening/intramolecular nucleophilic trapping of [n.1.0]-dibromocyclopropanes by tethered carboxylic acids results in cyclization to butyrolactones fused to six- and seven-membered carbocycles. In the case of bicyclic [4.3.0] lactones the cis-fused stereoisomer was formed, whereas for the bicyclic [5.3.0] lactones the trans-fused stereoisomer was formed. Optimal conditions for the reaction used silver­(I) trifluoroacetate (2.0 equiv) in trifluoroethanol or with added pyridine (2.0 equiv) and NaPF6 (5.0 equiv). The dibromocyclopropane precursors were made through cyclopropanation with in situ-generated dibromocarbene. The trans-fused lactones are potentially useful building blocks for pseudoguaianolide, guaianolide, and xanthanolide total synthesis. A computational study on the conformational preferences of these systems indicates that the trans-fused bicyclic [5.3.0] butyrolactones are lower in energy than the corresponding cis-fused lactones at the B3LYP/cc-pVTZ level of theory.