Though chiral pool synthesis is widely accepted as a powerful strategy in complex molecule synthesis, the effectiveness of the approach is intimately linked to the range of available chiral building blocks and the functional groups they possess. To date, there is still a pressing need for new remote functionalization methods that would allow the installation of useful chem-ical handles on these building blocks to enable a broader spectrum of synthetic manipulations. Herein, we report the engi-neering of a P450BM3 variant for the regioselective C–H oxidation of sclareol at C6. The synthetic utility of the resulting product was demonstrated in a formal synthesis of ansellone B and the first total synthesis of the 2,3-seco-labdane excolide B.
Supporting Information for Remote B-Ring Oxidation of Sclareol with an Engineered P450 Facilitates Divergent Access to Complex Terpenoids