The Development of Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling Chemistry

Glenn C. Micalizio, Haruki Mizoguchi

Research output: Contribution to journalReview articlepeer-review

14 Citations (Scopus)


Alkoxide-directed metallacycle-mediated cross-coupling is a rapidly growing area of reaction methodology in organic chemistry. Over the last decade, developments have resulted in more than thirty new and highly selective intermolecular (or “convergent”) C−C bond-forming reactions that have established powerful retrosynthetic relationships in stereoselective synthesis. While early studies were focused on developing transformations that forge a single C−C bond by way of a functionalized and unsaturated metallacyclopentane intermediate, recent advances mark the ability to employ this organometallic intermediate in additional stereoselective transformations. Among these more advanced coupling processes, those that embrace the metallacycle in subsequent [4+2] chemistry have resulted in the realization of a number of highly selective annulative cross-coupling reactions that deliver densely functionalized and angularly substituted carbocycles. This review discusses the early development of this chemistry, recent advances in reaction methodology, and shares a glimpse of the power of these processes in natural product synthesis.

Original languageEnglish
Pages (from-to)228-238
Number of pages11
JournalIsrael Journal of Chemistry
Issue number3
Publication statusPublished - Apr 1 2017
Externally publishedYes


  • [2+2+2] annulation
  • carbocycles
  • directed reaction
  • metallacycle-mediated cross-coupling
  • titanium

ASJC Scopus subject areas

  • Chemistry(all)


Dive into the research topics of 'The Development of Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling Chemistry'. Together they form a unique fingerprint.

Cite this