Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 48, Pages 21867-21871Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c10735
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Funding
- European Research Council (ERC)
- Deutsche Forschungsgemeinschaft [HE 7133/8-1]
- Boehringer Ingelheim Stiftung (plus3 perspectives program)
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This study discusses the formation mechanism of the anthrasteroid rearrangement and provides experimental evidence through chemical emulation from a plausible biogenetic precursor. The formation of asperfloketals A and B is shown to be achieved through double Wagner-Meerwein rearrangements, resulting in 1(10-*5),1(5 -*6)- and 1(10-*5),4(5-*6)diabeo-14,15- secosteroids, respectively. An efficient route to a bioinspired precursor is established by a sequence of orchestrated oxidative activation and rearrangement from ergosterol.
The anthrasteroid rearrangement has been discussed for the formation of the eponymous substance class since its discovery. We here report its chemical emulation from a plausible biogenetic precursor and show how it accounts for the formation of asperfloketals A and B through a mechanistic bifurcation event. As a result, these natural products arise from double Wagner- Meerwein rearrangements and, thus, are 1(10-*5),1(5 -*6)-and 1(10-*5),4(5-*6)diabeo-14,15-secosteroids, respectively. To establish an efficient route to a bioinspired precursor, we devised a sequence of orchestrated oxidative activation and rearrangement from ergosterol.
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