☆ 4.8 Article

Total Synthesis of Verruculogen and Fumitremorgin A Enabled by Ligand-Controlled C-H Borylation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 137, 期 32, 页码 10160-10163

出版社

AMER CHEMICAL SOC

DOI: 10.1021/jacs.5b07154

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Chemistry, Multidisciplinary

资金

NIH/NIGMS [GM-073949]
NSF
DAAD
JSPS
Grants-in-Aid for Scientific Research [14J03546] Funding Source: KAKEN

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摘要

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 N-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 N,C3-disubstituted indole for the synthesis of indole-containing natural products and pharmaceuticals.

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