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
摘要
介绍了 Ir 催化的具有高元对 F/CN 的氟化和氰化炔烃的 C-H 硼烷基化反应。使用二吡啶腙框架作为辅助配体和频哪醇硼烷 (HBpin) 作为官能化试剂生成的催化剂,对于缺电子和富电子底物的活性和选择性都明显高于 4,4′-二叔丁基-2,2′-联吡啶 (dtbpy)。通过对配体框架的研究,发现 HBpin 对腙进行了正式的 N-borylation,核磁共振光谱和 X 射线晶体学证明了这一点。随后,这种加合物与铱前催化剂发生了化学反应,生成了一种不同寻常的 IrI 酰肼。这种酰肼的分离和使用再现了原位生成催化剂的选择性,表明它导致了活性物种的形成。
A Hydrazone Ligand for Iridium-Catalyzed C–H Borylation: Enhanced Reactivity and Selectivity for Fluorinated Arenes
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.