Abstract
The [1,2]- and [2,3]-rearrangements of iodonium ylides are synthetically useful reactions for the generation of functionalized α-iodoesters. Allylic iodides are coupled with α-diazoesters in the presence of a copper catalyst and a ligand to generate iodonium ylides, which undergo metal-mediated rearrangements. By fine-tuning the structure of the ligand, we have reversed the regioselectivity of copper-catalyzed reactions of iodonium ylides from [2,3]- to [1,2]-rearrangements with the use of alternate bipyridine ligands. The preference for [1,2]-rearrangements was further improved by using bulky aryl α-diazoester substrates. Several α-iodoesters with a diverse range of functional groups were generated in good yields (up to 88% yield) and high regioselectivities (up to >95:5 regioisomeric ratio). A deuterium-labeled substrate was utilized to gain insight into the mechanism of the reaction.
Original language | English (US) |
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Pages (from-to) | 4150-4159 |
Number of pages | 10 |
Journal | Tetrahedron |
Volume | 73 |
Issue number | 29 |
DOIs | |
State | Published - 2017 |
Keywords
- Copper catalysis
- Deuterium labeling
- Iodine
- Iodonium ylide
- Ligand control
- Rearrangement
ASJC Scopus subject areas
- Biochemistry
- Drug Discovery
- Organic Chemistry