Regiodivergent photocyclization of dearomatized acylphloroglucinols: asymmetric syntheses of (—)-nemorosone and (—)-6-epi-garcimultiflorone A

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Date Issued
2019-07-17
Publisher Version
10.1021/jacs.9b05600
Author(s)
Wen, Saishuai
Boyce, Jonathan H.
Kandappa, Sunil K.
Sivaguru, Jayaraman
Porco, Jr., John A.
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https://hdl.handle.net/2144/40795
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Accepted manuscript
 
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Citation (published version)
Saishuai Wen, Jonathan H Boyce, Sunil K Kandappa, Jayaraman Sivaguru, John A Porco. 2019. "Regiodivergent photocyclization of dearomatized acylphloroglucinols: asymmetric syntheses of (—)-nemorosone and (—)-6-epi-garcimultiflorone A." J Am Chem Soc, Volume 141, Issue 28, pp. 11315 - 11321. https://doi.org/10.1021/jacs.9b05600
Abstract
Regiodivergent photocyclization of dearomatized acylphloroglucinol substrates has been developed to produce type A polycyclic polyprenylated acylphloroglucinol (PPAP) derivatives using an excited-state intramolecular proton transfer (ESIPT) process. Using this strategy, we achieved the enantioselective total syntheses of the type A PPAPs (—)-nemorosone and (—)-6-epi-garcimultiflorone A. Diverse photocyclization substrates have been investigated leading to divergent photocyclization processes as a function of tether length. Photophysical studies were performed, and photocyclization mechanisms were proposed based on investigation of various substrates as well as deuterium-labeling experiments.
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