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

Ian R. George | Zendy; Miguel LópezTena | Zendy; Anders Sundin | Zendy; Daniel Strand | Zendy

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

Author(s) -

Ian R. George,

Miguel LópezTena,

Anders Sundin,

Daniel Strand

Publication year - 2021

Publication title -

organic letters

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.94

H-Index - 239

eISSN - 1523-7060

pISSN - 1523-7052

DOI - 10.1021/acs.orglett.1c00955

Subject(s) - chemistry , cyanation , substituent , cyanohydrin , ketone , ether , selectivity , aryl , hydrolysis , alcohol , stereochemistry , combinatorial chemistry , organic chemistry , catalysis , alkyl

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 H 2 O 2 /H 3 O + 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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