Ascorbyl phloroglucinol 1a has previously only been isolated as the corresponding peracetate derivative 3. Prior work has also not been able to unambiguously assign the stereochemical configuration at the tertiary and hemiacetal carbons (C2′ and C3′) for any ascorbylated phenols, although modeling has suggested that the SSRS configuration for C2′–5′, respectively, is the most stable for 3.11 These intriguing biological data coupled with the interesting structures and open questions concerning the stability and stereochemistry of these molecules led us to pursue the development of a synthetic strategy to construct the tricyclic core of this set of related compounds.