The total synthesis of (-)-connatusin A, a hirsutane-type sesquiterpene isolated from the fungus Lentinus connatus BCC8996

Abstract

The title sesquiterpenoid natural product 1 has been prepared for the first time using the enantiomerically pure cis-1,2-dihydrocatechol 3 as starting material. Key steps associated with the synthesis include a Diels-Alder cycloaddition reaction of the acetonide 5 with cyclopentenone (4) and an oxa-di-π-methane rearrangement of bicylco[2.2.2]octenone 6 derived from the initial adduct. The product of this sequence, the cyclopropannulated triquinane 7, was elaborated, over a further eight steps including those involving Upjohn dihydroxylation and Swern oxidation protocols, to the target 1. A single-crystal X-ray analysis served to confirm the structure of this synthetically derived material. Show more