1. Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones
- Author
-
Alex M. Szpilman, Gulab Khushalrao Pathe, Keshaba Nanda Parida, and Shimon Maksymenko
- Subjects
Ketone ,ketones ,Trimethylsilyl ,enolonium species ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,Full Research Paper ,enolates ,Umpolung ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Reactivity (chemistry) ,lcsh:Science ,chemistry.chemical_classification ,010405 organic chemistry ,Organic Chemistry ,umpolung ,Enol ,0104 chemical sciences ,Chemistry ,hypervalent iodine ,chemistry ,Yield (chemistry) ,Enol ether ,lcsh:Q ,Organic synthesis ,1,4-diketones - Abstract
Due to their closely matched reactivity, the coupling of two dissimilar ketone enolates to form a 1,4-diketone remains a challenge in organic synthesis. We herein report that umpolung of a ketone trimethylsilyl enol ether (1 equiv) to form a discrete enolonium species, followed by addition of as little as 1.2–1.4 equivalents of a second trimethylsilyl enol ether, provides an attractive solution to this problem. A wide array of enolates may be used to form the 1,4-diketone products in 38 to 74% yield. Due to the use of two TMS enol ethers as precursors, an optimization of the cross-coupling should include investigating the order of addition.
- Published
- 2018
- Full Text
- View/download PDF