Enantioselective Total Synthesis of (–)‐Subglutinols A and B: Potential Immunosuppressive Agents Isolated from a Microorganism

Potential immunosuppressive diterpenoid pyrones (–)‐subglutinols A and B were efficiently synthesized in an enantioselective manner starting from a known trans ‐decalone derivative. The synthetic method involved the following key steps: (i) [2,3]‐Wittig rearrangement of a stannyl methyl ether to access the requisite decalin segment; (ii) coupling of the decalin segment with a γ‐pyrone moiety to set up the desired carbon framework; (iii) construction of a characteristic tetrahydrofuran ring in one‐pot fashion through an internal S N 2‐type cyclization, and (iv) conversion of a γ‐pyrone moiety into an α‐pyrone ring to yield the target (–)‐subglutinols A and B.