[3,3]-Sigmatropic rearrangements of propargyl alkynyl ethers. Synthesis of complex dienoates and unsaturated lactones

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 addi...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2023-02, Vol.21 (5), p.95-954
Main Authors: Sosa, Juan R, Tudjarian, Armen A, Minehan, Thomas G
Format: Article
Language:English
Subjects:
Aldehydes
Butanol
Ethers
Ketenes
Ketones
Lactones
Low temperature
Tert-butanol
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Summary: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. A low temperature [3,3]-sigmatropic rearrangement of in situ propargyl alkynyl ethers takes place to provide substituted dienoates and unsaturated lactones.
ISSN:1477-0520
1477-0539
DOI:10.1039/d2ob02121h