Bidirectional Total Synthesis of Phainanoid A via Strategic Use of Ketones

Here we report the total synthesis of phainanoid A, a unique dammarane-type triterpenoid (DTT), using an unusual bidirectional synthetic strategy. It features two transition-metal-mediated highly diastereoselective transformations to access the two challenging strained ring systems that branch toward opposite directions from the tricyclic core. This work also highlights the strategic use of ketones (or enol triflates) as versatile handles for rapid growth of molecular complexity in all key transformations, which paves the way for efficient preparations of complex and biologically significant DTTs.