Domino Heck-Diels-Alder reactions of monosubstituted bicyclopropylidenes

Baris Yucel, Mathias Noltemeyer, Armin De Meijere*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)


A three-component domino Heck-Diels-Alder reaction involving pinacol bicyclopropylideneboronate (8b), iodobenzene (9) and methyl acrylate (12) under Jeffery conditions [Pd(OAc)2, PPh3, K2CO 3, Et4NCl, MeCN] produced a mixture of phenylspiro[2.5]octeneboronates syn/anti-(E)-14b and methyl phenylspirooctenecarboxylate 25 in 25 and 38% yield, respectively. The major product 25 was most probably formed via the homoallylpalladium complex 23b undergoing deboropalladation rather than dehydropalladation. Similarly, reactions of tributylstannyl- and hydroxydimethylsilyl-substituted bicyclopropylidenes 8c-d with 9 and tert-butyl acrylate gave the tert-butyl phenylspirooctenecarboxylate 26 via the diene 24 formed by demetallopalladation processes. The reaction of methyl 1,1′-bicyclopropylidene-2-carboxylate (8e) with iodobenzene (9) in the presence of tert-butyl acrylate (13) furnished a mixture of regioisomeric and diastereomeric spirooctenes syn/anti-(E)-15e and syn/anti-(Z)-15e in 69 and 6% yield, respectively. The structures of the major pair of diastereomers syn-(E)-15e and anti-(E)-15e were rigorously proved by X-ray crystal structure analyses.

Original languageEnglish
Pages (from-to)1072-1078
Number of pages7
JournalEuropean Journal of Organic Chemistry
Issue number6
Publication statusPublished - Feb 2008


  • Bicyclopropylidene
  • Deboropalladation
  • Domino reactions
  • Heck coupling
  • Multicomponent reaction


Dive into the research topics of 'Domino Heck-Diels-Alder reactions of monosubstituted bicyclopropylidenes'. Together they form a unique fingerprint.

Cite this