Highly substituted homoallylvinylcyclopropanes by indium-mediated reaction of alpha,beta-unsaturated ketones and aldehydes with allylic halides

SM Capps, TP Clarke, JPH Charmant, HAF Hoppe, GC Lloyd-Jones*, M Murray, TM Peakman, RA Stentiford, KE Walsh, PA Worthington

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

Allylindium reagents, prepared from excess allylic halide (Br or I) and indium metal, react with alpha,beta-unsaturated ketones and aldehydes to give, after aerobic acidic workup, homoallyl-substituted vinylcyclopropanes. This process was explored and developed after a chance discovery arising from a side reaction in an attempted Pd-catalysed process. The structure of the cyclopropane arising from the reaction of bis(p-chlorobenzylidine)acetone was confirmed by X-ray crystallography. Whilst bis-alpha,beta-unsaturated ketones give rise to a single homoallylcyclopropane species, alpha,beta-unsaturated ketones and aldehydes give diastereomeric mixtures whose relative stereochemistry were assigned by NOE experiments. Crotylindium reagents react with good to perfect regioselectivity to afford tetrasubstituted cyclopropanes but prenylindium reagents fail to generate the analogous pentasubstituted rings.

Original languageEnglish
Pages (from-to)963-974
Number of pages12
JournalEuropean Journal of Organic Chemistry
Issue number6
Publication statusPublished - Mar 2000

Keywords / Materials (for Non-textual outputs)

  • indiumallyl compounds
  • vinylcyclopropanes
  • alpha,beta-unsaturated carbonyl compounds
  • diastereoselectivity
  • dibenzylideneacetone
  • AQUEOUS-MEDIA
  • CARBONYL-COMPOUNDS
  • DIBENZYLIDENE ACETONE
  • STEREOSELECTIVE SYNTHESIS
  • ORGANOINDIUM REAGENTS
  • OXIDATIVE ADDITION
  • ORGANIC-SYNTHESIS
  • ALLYLATION
  • ALKYLATION
  • COMPLEXES

Fingerprint

Dive into the research topics of 'Highly substituted homoallylvinylcyclopropanes by indium-mediated reaction of alpha,beta-unsaturated ketones and aldehydes with allylic halides'. Together they form a unique fingerprint.

Cite this