Hongyu Zhong

Last Name

Zhong

First Name

Hongyu

ORCID

0000-0002-6892-482X

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Publications 1 - 6 of 6

Synthesis and Reversible H2 Activation by Coordinatively Unsaturated Rhodium NHC Complexes
Lutz, Marius; Zhong, Hongyu; Trapp, Nils; et al. (2023)
Helvetica Chimica Acta
We report the synthesis of coordinatively unsaturated cationic rhodium complexes bearing the sterically encumbered electron-rich NHC ligand IPr*OMe. The COD (1,5-cyclooctadiene) complex [Rh(IPr*OMe)(COD)]BF4 adopts a tilted, pseudo-square planar coordination geometry, where bonding to the ipso-carbon of the NHC aryl substituent was observed in the solid state. Hydrogenation of this complex afforded a metastable dihydride complex [Rh(IPr*OMe)(H)2]BF4 with an unusual internal coordination to an arene of the ligand. In the absence of a hydrogen atmosphere, spontaneous reductive elimination of H2 afforded a rhodium complex [Rh(IPr*OMe)]BF4 with a single chelating ligand that stabilizes the highly unsaturated metal by two-fold π-face donation as suggested by NMR spectroscopy and computational studies. This unusual complex might serve as a versatile precatalyst for a variety of transformations.
Carbon-carbon bond formation in reverse
Zhong, Hongyu; Morandi, Bill (2022)
Nature Synthesis
The reversible formation of carbon–carbon bonds is key in many catalytic reactions but its mechanism is challenging to study. Now, a detailed investigation into a palladium-catalysed diastereoconvergent reaction uncovers a unique mechanism in which reversible β-carbon elimination is crucial for productive catalysis.
Nickel-Catalyzed Enantioselective Hydrothiocarbonylation of Cyclopropenes
Cai, Song-Zhou; Yu, Rongrong; Li, Can; et al. (2023)
Organic Letters
Hydrothiocarbonylation of olefins using carbon monoxide and thiols is a powerful method to synthesize thioesters from simple building blocks. Owing to the intrinsic challenges of catalyst poisoning, transition-metal-catalyzed asymmetric thiocarbonylation, particularly when utilizing earth abundant metals, remains rare in the literature. Herein, we report a nickel-catalyzed enantioselective hydrothiocarbonylation of cyclopropenes for the synthesis of a diverse collection of functionalized thioesters in good to excellent yields with high stereoselectivity. This new method employs an inexpensive, air-stable nickel(II) precursor, which provides enhanced catalyst fidelity against CO poisoning compared to nickel(0) catalysts.
One-Step Process for the Regiodivergent Double Hydrocyanation of 1,3-Butadiene
Long, Jinguo; Wang, Ting; Zhong, Hongyu; et al. (2025)
Angewandte Chemie. International Edition
In industry, the two important nitrile starting materials, adiponitrile and 2-methylglutaronitrile, are primarily manufactured through the well-known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel-catalyzed divergent, one-step double hydrocyanation of 1,3-butadiene to produce either adiponitrile or 2-methylglutaronitrile in high regioselectivity. The key to this success lies in the highly tunable binding pockets of the bidentate phosphite ligands, which creates a geometrically defined coordination space around the nickel center. The first hydrocyanation that produces either the linear or branched alkenyl nitrile was identified as the selectivity-determining step. Organometallic studies confirm the formation of well-defined diphosphite nickel diene complexes in solution, and the role of ligands in dictating regioselectivity was further rationalized by DFT computations. This result provides the first example of a highly selective nickel-catalyzed synthesis of adiponitrile and 2-methylglutaronitrile from butadiene, and it also represents a high-level of catalyst-controlled regioselectivity via the fine-tuning of ligand pocket geometry.
Escaping from directing groups: Enantioselective C-C bond construction from unactivated olefins
Zhong, Hongyu; Morandi, Bill (2024)
Science Bulletin
Skeletal metalation of lactams through a carbonyl-to-nickel-exchange logic
Zhong, Hongyu; Egger, Dominic T.; Gasser, Valentina; et al. (2023)
Nature Communications
Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending the metal-halogen exchange logic to a metal-carbon exchange would enable the direct modification of carbon frameworks with new implications in retrosynthetic analysis. However, such a transformation requires the selective cleavage of highly inert chemical bonds and formation of stable intermediates amenable to further synthetic elaborations, hence its development has remained considerably challenging. Here we introduce a skeletal metalation strategy that allows lactams, a prevalent motif in bioactive molecules, to be readily converted into well-defined, synthetically useful organonickel reagents. The reaction features a selective activation of unstrained amide C–N bonds mediated by an easily prepared Ni(0) reagent, followed by CO deinsertion and dissociation under mild room temperature conditions in a formal carbonyl-to-nickel-exchange process. The underlying principles of this unique reactivity are rationalized by organometallic and computational studies. The skeletal metalation is further applied to a direct CO excision reaction and a carbon isotope exchange reaction of lactams, underscoring the broad potential of metal-carbon exchange logic in organic synthesis.

Publications 1 - 6 of 6

Hongyu Zhong

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