期刊
NATURE CHEMISTRY
卷 9, 期 10, 页码 944-949出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/NCHEM.2801
关键词
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资金
- NIH-NIGMS [R01 GM090007]
- Dreyfus Foundation
- UCLA Gold Shield Alumnae
- National Science Foundation Graduate Research Fellowship Program [DGE-1144087]
- University of California, Los Angeles
- NSF [CHE-1048804]
- National Center for Research Resources [S10RR025631]
Tubingensin B is an indole diterpenoid that bears a daunting chemical structure featuring a disubstituted carbazole unit, five stereogenic centres-three of which are quaternary-and a decorated [3.2.2]-bridged bicycle. We describe our synthetic design toward a concise and enantiospecific total synthesis of tubingensin B, which hinges on the strategic use of a transient aryne intermediate. Although initial studies led to unexpected reaction outcomes, we ultimately implemented a sequence of carbazolyne cyclization followed by Rh-catalysed fragmentation to install the seven-membered ring and vicinal quaternary stereocentres of the natural product. Coupled with a late-stage radical cyclization to construct the [3.2.2]-bridged bicycle, these efforts have enabled the total synthesis of tubingensin B. The design and evolution of our succinct total synthesis underscores the utility of long-avoided aryne intermediates for the introduction of structural motifs that have conventionally been viewed as challenging.
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