Stereoselective Total Synthesis of (±)-Pleurospiroketals A and B

A full account of our efforts toward the stereoselective total synthesis of sesquiterpenoid-derived natural products (±)-pleurospiroketals A and B is described. Commercially available 3-methyl-2-cyclohexenone and 2,2-dimethyloxirane were used as key building blocks, and the substrate-controlled ster...

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Published inJournal of organic chemistry Vol. 86; no. 19; pp. 13572 - 13582
Main Authors Thorat, Sagar S, Rama Krishna, Gamidi, Kontham, Ravindar
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 01.10.2021
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
MILD
ACID
REMOVAL
REDUCTION
CONSTRUCTION
CASCADE ANNULATION
DERIVATIVES
ALKYNOLS
ACCESS
CYCLIZATION
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Summary:A full account of our efforts toward the stereoselective total synthesis of sesquiterpenoid-derived natural products (±)-pleurospiroketals A and B is described. Commercially available 3-methyl-2-cyclohexenone and 2,2-dimethyloxirane were used as key building blocks, and the substrate-controlled stereoselection was exploited to access the entire stereochemistry of these natural products. Initially, a planned synthetic route involving a [6,5]-bicyclic lactone intermediate was found to be insurmountable, and the later strategy comprising OsO4-NMO-mediated dihydroxylation of 3-methyl-2-cyclohexenone, followed by Luche reduction, Eschenmoser methylenation, and Brønsted acid-induced spiroketalization steps, was ultimately identified as the reliable strategy.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.1c01634