Synthesis of (+)-Pancratistatins via Catalytic Desymmetrization of Benzene

A concise synthesis of (+)-pancratistatin
and (+)-7-deoxypancratistatin
from benzene using an enantioselective, dearomative carboamination
strategy has been achieved. This approach, in combination with the
judicious choice of subsequent olefin-type difunctionalization reactions,
permits rapid and controlled access to a hexasubstituted core. Finally,
minimal use of intermediary steps as well as direct, late stage C-7
hydroxylation provides both natural products in six and seven operations.