Christopher D. Peruzzi, Susanne L. Miller, Jonathan E. Dannatt, Behnaz Ghaffari, Robert E. Maleczka Jr.* and Milton R. Smith III*,
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引用次数: 0
Abstract
Ir-catalyzed C–H borylations of fluorinated and cyanated arenes with high meta-to-F/CN are described. Use of a dipyridyl hydrazone framework as the ancillary ligand and pinacolborane (HBpin) as the functionalizing reagent generates catalysts that are significantly more active and selective than 4,4′-di-tert-butyl-2,2′-bipyridine (dtbpy) for both electron-deficient and electron-rich substrates. Investigation of the ligand framework resulted in the observation of formal N-borylation of the hydrazone by HBpin, as evidenced by NMR spectroscopy and X-ray crystallography. Subsequent stoichiometric reactions of this adduct with an iridium precatalyst revealed the formation of an unusual IrI hydrazido. Isolation and use of this hydrazido reproduce the selectivity of insitu generated catalysts, suggesting that it leads to formation of the active species.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.