Synthesis of 2,2-Dialkyl Chromanes by Intramolecular Ullmann C-O Coupling Reactions toward the Total Synthesis of D-alpha-Tocopherol

The complete synthesis of D-alpha-tocopherol was achieved using our developed-Ullmann C-O coupling reaction as a key reaction. The synthesis of the core structure of D-alpha-tocopherol, which is a chiral chromane, has never been reported using intramolecular Ullmann C-O coupling reactions owing to the low reactivity of electron-rich iodoarenes with tertiary alcohols. Because the developed intramolecular C-O coupling reactions prefer electron-rich iodoarenes with tertiary alcohols, we successfully synthesized the chiral chromane core and achieved the total synthesis of D-alpha-tocopherol.