Enantioselective Total Syntheses of Manginoids A and C and Guignardones A and C

An enantioselective synthetic approach for preparing manginoids and guignardones, two types of biogenetically related meroterpenoids, is reported. This bioinspired and divergent synthesis employs an oxidative 1,3‐dicarbonyl radical‐initiated cyclization and cyclodehydration of the common precursor t...

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Published inAngewandte Chemie International Edition Vol. 60; no. 28; pp. 15286 - 15290
Main Authors Zong, Yan, Xu, Ze‐Jun, Zhu, Rong‐Xiu, Su, Ai‐Hong, Liu, Xu‐Yuan, Zhu, Ming‐Zhu, Han, Jing‐Jing, Zhang, Jiao‐Zhen, Xu, Yu‐Liang, Lou, Hong‐Xiang
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 05.07.2021
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
asymmetric synthesis
Chemistry
Chemistry, Multidisciplinary
cyclization
Divergence
Enantiomers
meroterpenoid
natural products
Physical Sciences
Science & Technology
Silica
Silica gel
Silicon dioxide
total synthesis
natural products
asymmetric synthesis
STRATEGY
DIVERGENT SYNTHESIS
total synthesis
MEROTERPENOIDS
cyclization
meroterpenoid
ASYMMETRIC TOTAL-SYNTHESIS
DERIVATIVES
FLOWERS
Natural products
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Summary:An enantioselective synthetic approach for preparing manginoids and guignardones, two types of biogenetically related meroterpenoids, is reported. This bioinspired and divergent synthesis employs an oxidative 1,3‐dicarbonyl radical‐initiated cyclization and cyclodehydration of the common precursor to forge the central ring of the manginoids and guignardones, respectively, at a late stage. Key synthetic steps include silica‐gel‐promoted semipinacol rearrangement to form the 6‐oxabicyclo[3.2.1]octane skeleton and the Suzuki–Miyaura reaction of vinyl bromide to achieve fragment coupling. This synthesis protocol enables the asymmetric syntheses of four fungal meroterpenoids from commercially available materials. The enantioselective total syntheses of fungal meroterpenoids, manginoids A and C, as well as guignardones A and C, are accomplished. This divergent and bioinspired synthetic strategy involves a Csp3−Csp2 Suzuki–Miyaura coupling of vinyl bromide, silica‐gel‐promoted semipinacol rearrangement, and oxidative 1,3‐dicarbonyl radical‐initiated cyclization.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202104182