Feng, Yu Holte, Dane Zoller, Jochen Umemiya, Shigenobu Simke, Leah R. Baran, Phil S. Total Synthesis of Verruculogen and Fumitremorgin A Enabled by Ligand-Controlled C–H Borylation Verruculogen and fumitre­morgin A are bioactive alkaloids that contain a unique eight-membered endo­peroxide. Although related natural products such as fumitre­morgins B and C have been previously synthesized, we report the first synthesis of the more complex, endo­peroxide-containing members of this family. A concise route to verruc­ulogen and fumitre­morgin A relied not only on a hydroperoxide/indole hemiaminal cyclization, but also on the ability to access the seemingly simple starting material, 6-methoxy­tryptophan. An iridium-catalyzed C–H borylation/Chan–Lam procedure guided by an <i>N</i>-TIPS group enabled the conversion of a tryptophan derivative into a 6-methoxy­tryptophan derivative, proving to be a general way to functionalize the C6 position of an <i>N</i>,C3-disubstituted indole for the synthesis of indole-containing natural products and pharmaceuticals. bioactive alkaloids;C 6 position;methoxy;synthesis;endo;fumitre;Total Synthesis 2015-08-19
    https://acs.figshare.com/articles/journal_contribution/Total_Synthesis_of_Verruculogen_and_Fumitremorgin_A_Enabled_by_Ligand_Controlled_C_H_Borylation/2139988
10.1021/jacs.5b07154.s001