A Hydrazone Ligand for Iridium-Catalyzed C-H Borylation: Enhanced Reactivity and Selectivity for Fluorinated Arenes.

Autor:	Peruzzi CD; Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States., Miller SL; Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States., Dannatt JE; Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States.; Department of Chemistry, University of Dallas, 1845 East Northgate Drive, Irving, Texas 75062, United States., Ghaffari B; Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States., Maleczka RE Jr; Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States., Smith MR 3rd; Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States.
Jazyk:	angličtina
Zdroj:	Organometallics [Organometallics] 2024 May 20; Vol. 43 (11), pp. 1208-1212. Date of Electronic Publication: 2024 May 20 (Print Publication: 2024).
DOI:	10.1021/acs.organomet.4c00174
Abstrakt:	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 Ir I hydrazido. Isolation and use of this hydrazido reproduce the selectivity of in situ generated catalysts, suggesting that it leads to formation of the active species. Competing Interests: The authors declare the following competing financial interest(s): S.L.M., M.R.S., and R.E.M. own a percentage of BoroPharm, Inc. (© 2024 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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