Modulable and highly diastereoselective carbometalations of cyclopropenes

Dorian Didier, Pierre Olivier Delaye, Marwan Simaan, Biana Island, Guillaume Eppe, Hendrik Eijsberg, Amir Kleiner, Paul Knochel, Ilan Marek

Research output: Contribution to journalArticlepeer-review

Abstract

The copper-catalyzed carbomagnesiation reaction of cyclopropenyl esters 1 leads to various substituted cyclopropanes species 3 in good yields with very high diastereoselectivities. The reaction proceeds through a syn-chelated carbomagnesiation reaction and could be extended to various cyclopropenylmethyl ester derivatives 5. The potential of this approach was illustrated by the preparation of two consecutive all-carbon quaternary stereocenters. However, the carbometalation reaction needs to be performed at temperature ranging from -35 to -20 °C to avoid subsequent fragmentation reaction into stereodefined β,γ-nonconjugated unsaturated esters 4. Alternatively, the carbocupration reaction with organocopper species could also be performed to leads to configurationally stable cyclopropyl copper species 2[Cu]. Additionally, when the Lewis acid character of the copper center is decreased (i.e., RCuCNLi), the reaction proceed with an anti-selectivity. The diastereodivergent behavior of these organometallic species is of synthetic interest, since both diastereomers syn-3 and anti-3 can be obtained, at will, from the same precursor cyclopropenyl esters 1.

Original languageEnglish
Pages (from-to)1038-1048
Number of pages11
JournalChemistry - A European Journal
Volume20
Issue number4
DOIs
StatePublished - 20 Jan 2014

Keywords

  • carbometalation
  • chelation
  • copper
  • cyclopropene
  • diastereodivergence

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Modulable and highly diastereoselective carbometalations of cyclopropenes'. Together they form a unique fingerprint.

Cite this