Copper-catalyzed [1,2]-rearrangements of allylic iodides and aryl α-diazoacetates

Bin Xu, Jackson A. Gartman, Uttam K. Tambar

Research output: Contribution to journalArticle

2 Scopus citations

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 languageEnglish (US)
Pages (from-to)4150-4159
Number of pages10
JournalTetrahedron
Volume73
Issue number29
DOIs
StatePublished - 2017

Keywords

  • Copper catalysis
  • Deuterium labeling
  • Iodine
  • Iodonium ylide
  • Ligand control
  • Rearrangement

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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