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Zirconocene‐Mediated Carbonylative Coupling of Grignard Reagents


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.

Ein inklusiver Ansatz: Acylzirconocene [Cp2ZrCl(COR)] sind wertvolle Acylanionen‐Äquivalente in der Synthesechemie. Klassisch werden sie durch die Hydrozirconierung von Alkenen oder Alkinen hergestellt, was die Erzeugung von Aryl‐, Benzyl‐, tertiären Alkyl‐ oder verzweigten Acylzirconocenen ausschließt. Eine Zirconium‐vermittelte carbonylierende Kupplung von Grignard‐Reagentien wird nun beschrieben, die diese bislang unzugänglichen Zirconocen‐Intermediate beinhaltet.

Authors:   Melissa Moss, Xinping Han, Joseph M. Ready
Journal:   Angewandte Chemie
Year:   2016
Pages:   n/a
DOI:   10.1002/ange.201603133
Publication date:   13-Jul-2016
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