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A Unifying Bioinspired Synthesis of (-)-Asperaculin A and (-)-Penifulvin D

George, Ian R. LU ; Lopez-Tena, Miguel ; Sundin, Anders P. LU and Strand, Daniel LU (2021) In Organic Letters 23(9). p.3536-3540
Abstract

The first syntheses of the isomeric dioxafenestrene natural products (-)-asperaculin A and (-)-penifulvin D are reported. Each target is formed selectively by choice of oxidant in a final divergent bioinspired Baeyer-Villiger (BV) reaction. Density functional theory calculations reveal that electrostatic interactions between the oxidant leaving group and the lactone motif accounts for a reversal of selectivity with H2O2/H3O+ compared to peracids. Synthetic features include forging the polycyclic carbon framework with a diastereoselective meta-photocycloaddition biased by an ether substituent at the aryl α-position. The encumbered tertiary alcohol was installed by cyanation of a ketone intermediate followed by nonaqueous hydrolysis of... (More)

The first syntheses of the isomeric dioxafenestrene natural products (-)-asperaculin A and (-)-penifulvin D are reported. Each target is formed selectively by choice of oxidant in a final divergent bioinspired Baeyer-Villiger (BV) reaction. Density functional theory calculations reveal that electrostatic interactions between the oxidant leaving group and the lactone motif accounts for a reversal of selectivity with H2O2/H3O+ compared to peracids. Synthetic features include forging the polycyclic carbon framework with a diastereoselective meta-photocycloaddition biased by an ether substituent at the aryl α-position. The encumbered tertiary alcohol was installed by cyanation of a ketone intermediate followed by nonaqueous hydrolysis of the resulting delicate cyanohydrin.

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author
; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organic Letters
volume
23
issue
9
pages
3536 - 3540
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:33830776
  • scopus:85104928263
ISSN
1523-7060
DOI
10.1021/acs.orglett.1c00955
language
English
LU publication?
yes
id
7451456f-ea44-4d75-8ba8-163a73a593af
date added to LUP
2021-05-10 11:54:17
date last changed
2025-04-06 15:48:58
@article{7451456f-ea44-4d75-8ba8-163a73a593af,
  abstract     = {{<p>The first syntheses of the isomeric dioxafenestrene natural products (-)-asperaculin A and (-)-penifulvin D are reported. Each target is formed selectively by choice of oxidant in a final divergent bioinspired Baeyer-Villiger (BV) reaction. Density functional theory calculations reveal that electrostatic interactions between the oxidant leaving group and the lactone motif accounts for a reversal of selectivity with H2O2/H3O+ compared to peracids. Synthetic features include forging the polycyclic carbon framework with a diastereoselective meta-photocycloaddition biased by an ether substituent at the aryl α-position. The encumbered tertiary alcohol was installed by cyanation of a ketone intermediate followed by nonaqueous hydrolysis of the resulting delicate cyanohydrin. </p>}},
  author       = {{George, Ian R. and Lopez-Tena, Miguel and Sundin, Anders P. and Strand, Daniel}},
  issn         = {{1523-7060}},
  language     = {{eng}},
  number       = {{9}},
  pages        = {{3536--3540}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Organic Letters}},
  title        = {{A Unifying Bioinspired Synthesis of (-)-Asperaculin A and (-)-Penifulvin D}},
  url          = {{http://dx.doi.org/10.1021/acs.orglett.1c00955}},
  doi          = {{10.1021/acs.orglett.1c00955}},
  volume       = {{23}},
  year         = {{2021}},
}