title: Zirconocene-Mediated Carbonylative Coupling of Grignard Reagents.
abstract: Organozirconocenes are versatile synthetic intermediates that can undergo carbonylation to yield acyl anion equivalents. Zirconocene hydrochloride ([Cp2 ZrHCl]) 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.
authors.affiliation: Department of Biochemistry, Division of Chemistry, UT Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas, 75390-0938, USA.
authors.forename: Melissa
authors.initials: M
authors.lastname: Moss
authors.affiliation: Department of Biochemistry, Division of Chemistry, UT Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas, 75390-0938, USA.
authors.forename: Xinping
authors.initials: X
authors.lastname: Han
authors.affiliation: Department of Biochemistry, Division of Chemistry, UT Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas, 75390-0938, USA. joseph.ready@utsouthwestern.edu.
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Ready
mesh_terms: D001577:Benzophenones / Q000138:chemical synthesis* / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
chemical_list: D001577:Benzophenones; D009942:Organometallic Compounds; C023398:Zirconocene dichloride; D002248:Carbon Monoxide; D015040:Zirconium
keywords: carbonylation; carbonylative coupling; iodonium salts; isomerization; zirconium complexes