Transition Metal-Catalyzed Reactions of Methylenecyclopropanes

Itaru Nakamura, Yoshinori Yamamoto

Research output: Contribution to journalReview articlepeer-review

358 Citations (Scopus)

Abstract

The transition metal-catalyzed formal [3 + 2] cycloaddition of methylenecyclopropanes with unsaturated compounds X=Y, such as alkenes, aldehydes, and imines, gives five-membered carbocycles or heterocycles. The Heck-type reaction of R-Pd-X with the exomethylene part of methylenecyclopropanes gives the corresponding cyclopropylcarbinylpalladium complexes which undergo further transformations through typical palladium reactions such as β-hydride elimination or reductive elimination of Pd(0). Hydrostannation, hydrosilylation, hydrocarbonation, hydroamination, and hydroalkoxylation of methylenecyclopropanes proceed through the addition of the metal hydrides (H-M) and pronucleophiles (H-Nu) to the olefinic part, and the resulting intermediates are converted to the allylic products in which the homologation by three carbon atoms takes place from M and Nu, respectively. Bismetallation produces 1,3-bimetallic derivatives through metallacyclobutane intermediates.

Original languageEnglish
Pages (from-to)111-129
Number of pages19
JournalAdvanced Synthesis and Catalysis
Volume344
Issue number2
DOIs
Publication statusPublished - 2002 Apr

Keywords

  • Catalytic reaction
  • Hydroamination
  • Hydrocarbonation
  • Methylenecyclopropane
  • Transition metals (late)

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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