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A genetically modified fungal strain generated a natural product library used to conduct various activity screens for Alzheimer's disease tau aggregation. The hit compound, penicillic acid, was optimized for the development of analogs.more » « lessFree, publicly-accessible full text available December 11, 2025
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Baeyer-Villiger oxidation of alpha-alkoxy ketones 1 provides lactone acetals 2, which react with the lithium salts of di-methyl(alkyl) phosphonates in the presence of LaCl3•2LiCl to provide cyclic enones 3 in good to excellent yields after treatment with dilute aqueous potassium carbonate. Thus, five-, six-, and seven-membered lactones are con-verted to five-, six-, and seven membered cyclic enones. The utility of this two-step ring expansion method is demonstrated in the synthesis of (±)-1-epi-xerantholide from 5-methyl-2-cyclohexen-1-one.more » « less
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In an extension of our studies on low-temperature rearrangements of 1-alkynyl ethers, we describe herein the [3,3]-sigmatropic rearrangement of in situ formed propargyl alkynyl ethers to allenyl ketenes, which furnish complex tert -butyl-(2 E ,4 Z )-dienoates 2 in good yields upon tert -butanol addition. Similarly, sigmatropic rearrangements of in situ formed propargyl lithioalkynyl ethers yield methyl-(2 Z ,4 Z )-dienoates 4 upon methanol addition or unsaturated lactones 6 upon aldehyde or ketone addition to the allenyl ynolate intermediate.more » « less
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