Syntheses Of (+)-30-Epi-, (-)-6-Epi-, (+/-)-6,30-Epi-13,14-Didehydroxyisogarcinol And (+/-)-6,30-Epi-Garcimultiflorone A Utilizing Highly Diastereoselective, Lewis Acid-Controlled Cyclizations

The first syntheses of 13,14-didehydroxyisogarcinol (6) and garcimultiflorone A (5) stereoisomers are reported in six steps from a commercially available phloroglucinol. Lewis acid-controlled, diastereoselective cationic oxycyclizations enabled asymmetric syntheses of (-)-6-epi-6 and (+)-30-epi-6. A similar strategy enabled production of the meso-dervied isomers (+/-)-6,30-epi-6 and (+/-)-6,30-epi-5. Finally, a convenient strategy for gram scale synthesis was developed utilizing diastereomer separation at a later stage in the synthesis that minimized the number of necessary synthetic operations to access all possible stereoisomers.