Zirconocene-Mediated Carbonylative Coupling of Grignard Reagents

Melissa Moss, Xinping Han, Joseph M. Ready

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Organozirconocenes are versatile synthetic intermediates that can undergo carbonylation to yield acyl anion equivalents. Zirconocene hydrochloride ([Cp2ZrHCl]) is often the reagent of choice for accessing these intermediates but generates organozirconocenes only from alkenes and alkynes. This requirement eliminates a broad range of substrates. For example, organozirconocenes in which the zirconium center is bonded to an aromatic ring, a benzylic group, or an alkyl group that possesses a tertiary or quaternary carbon atom α to the carbon–zirconium bond can not be formed in this way. To provide more generalized access to acyl zirconium reagents, we explored the transmetalation of Grignard reagents with zirconocene dichloride under a CO atmosphere. This protocol generates acyl zirconium(IV) complexes that are inaccessible with the Schwartz reagent, including those derived from secondary and tertiary alkyl and aryl Grignard reagents.

Original languageEnglish (US)
Pages (from-to)10017-10021
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number34
DOIs
StatePublished - Aug 16 2016

Fingerprint

Zirconium
Carbonylation
Olefins
Alkynes
Alkenes
Negative ions
Carbon Monoxide
Anions
Atoms
Carbon
Substrates
Zirconocene dichloride

Keywords

  • carbonylation
  • carbonylative coupling
  • iodonium salts
  • isomerization
  • zirconium complexes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Zirconocene-Mediated Carbonylative Coupling of Grignard Reagents. / Moss, Melissa; Han, Xinping; Ready, Joseph M.

In: Angewandte Chemie - International Edition, Vol. 55, No. 34, 16.08.2016, p. 10017-10021.

Research output: Contribution to journalArticle

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