AI Article Synopsis
- - α,β-Unsaturated carbonyls are important for targeting proteins related to diseases, with various methods for adding stereoselective functional groups at the α-position, like Morita-Baylis-Hillman and Negishi reactions.
- - The text outlines a new approach to α-homoallylation of cyclic enones, which involves a series of reactions including conjugate addition and a unique rearrangement that maintains chirality.
- - A key highlight is the use of a photocatalyzed reaction that enhances stereocontrol at the exo-β-position, allowing effective use of allyl groups in synthetic processes.
Article Abstract
α,β-Unsaturated carbonyls are essential structural motifs for nucleophiles of disease-related proteins. Methods for stereoselective functionalizations at the α-position include the Morita-Baylis-Hillman, Negishi, Sonogashira, Stille, and Rauhut-Currier reactions. Described here is a method for the diastereodivergent α-homoallylation of cyclic enones via a sequence of conjugate addition, aldol condensation, and diastereoselective [3,3]-sigmatropic rearrangement. Mechanistic investigations revealed that the [3,3]-sigmatropic rearrangement proceeds with transfer of chirality. These inspire a photocatalyzed olefin isomerization of the aldol condensation product leading to a highly diastereoselective [3,3]-sigmatropic rearrangement to furnish the α-homoallylation of cyclic enones. Importantly, this photocatalyzed olefin isomerization/diastereoselective [3,3]-sigmatropic rearrangement reaction sequence permits a full stereocontrol of the exo-β-position featuring an allyl group as a synthetic functional handle.
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| http://dx.doi.org/10.1021/acs.orglett.3c04151 | DOI Listing |
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