Tandem nickel-catalyzed reductive cyclization-coupling enables divergent total syntheses of yatein, sumatranin A, isodeoxypodophyllotoxin and isostegane.

Herein, we report a divergent approach for the total synthesis of polycyclic lignans yatein (1), sumatranin A (2), isodeoxypodophyllotoxin (3) and isostegane (4) from dibenzyltetrahydrofuran acetals, which could be constructed by the nickel-catalyzed tandem reductive cyclization-coupling as a key step. These advanced intermediates were readily converted to yatein and sumatranin A via an oxidation reaction or acid-mediated cyclization, respectively. Subsequently, the six- or eight-membered carbon ring in isodeoxypodophyllotoxin or isostegane could be constructed through a reagent-controlled regioselective oxidative coupling reaction of yatein.