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Stereoselective Approach to Multisubstituted Enolates from Unactivated Alkynes: Oxyalkylidenation of Alkynyl Ketone Enolates with Aldehydes
Abstract
The preparation of multisubstituted enolates with precise regio- and stereocontrol is a nontrivial task when conventional deprotonation methods are used on the corresponding carbonyl compounds. We describe herein an approach to preparing stereodefined enolates by leveraging the stereoselective oxyfunctionalization of unactivated alkynes, particularly in the context of the alkynylogous aldol reaction. trans-Iodo(III)acetoxylation of alkynes and subsequent Sonogashira coupling allow for the facile preparation of multisubstituted enynyl acetates, which can be deacetylated by MeLi into the corresponding enolates. The alkynyl enolates react with aldehydes to afford γ,δ-unsaturated β-diketones through a cascade of alkynylogous aldol addition, intramolecular Michael addition, and ring opening of the oxetene intermediate- Text
- Journal contribution
- Biophysics
- Biochemistry
- Genetics
- Plant Biology
- Computational Biology
- Space Science
- Mathematical Sciences not elsewhere classified
- Chemical Sciences not elsewhere classified
- intramolecular michael addition
- conventional deprotonation methods
- alkynylogous aldol reaction
- alkynylogous aldol addition
- preparing stereodefined enolates
- alkynyl ketone enolates
- alkynyl enolates react
- multisubstituted enynyl acetates
- corresponding carbonyl compounds
- multisubstituted enolates
- corresponding enolates
- unsaturated β
- trans </
- stereoselective oxyfunctionalization
- ring opening
- precise regio
- oxetene intermediate
- nontrivial task
- describe herein
- afford γ
- >- iodo