Synthesis of 6‑Substituted 2‑Pyrones Starting from Renewable Resources: Total Synthesis of Sibirinone, (E)‑6-(Pent-1-en-1-yl)‑2H‑pyran-2-one, and (E)‑6-(Hept-1-en-1-yl)‑2H‑pyran-2-one

An atom-economic reaction sequence to 6-substituted 2-pyrones was developed starting from furfuryl alcohol, a renewable resource made from bran or bagasse, and aldehydes, utilizing a thermal rearrangement of cyclopentadienone epoxides as key step. Derivatives bearing a hydroxyalkyl side chain could be enzymatically resolved, providing access to enantiomerically pure 2-pyrones, or converted to alkenyl-substituted 2-pyrones such as naturally occurring sibirinone, (E)-6-(pent-1-en-1-yl)-2H-pyran-2-one, and (E)-6-(hept-1-en-1-yl)-2H-pyran-2-one.