[reaction: see text] Various ferrocene-based organosilanols have been synthesized in four steps starting from achiral ferrocene carboxylic acid. Applying these novel planar-chiral ferrocenes as catalysts in asymmetric phenyl transfer reactions to substituted benzaldehydes afforded products with high enantiomeric excesses. The best result (91% ee) was achieved in the addition to p-chlorobenzaldehyde with organosilanol 2b, which has a tert-butyl substituent on the oxazoline ring and an isopropyl group on the silanol fragment.
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http://dx.doi.org/10.1021/ol050242+ | DOI Listing |
Chem Soc Rev
January 2025
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
For decades, advances in chiral transition metal catalysis have been closely tied to the development of customized chiral ligands. Recently, however, an alternative approach to this traditional metal-plus-chiral-ligand method has emerged. In this new strategy, chiral transition metal catalysts are composed entirely of achiral ligands, with the overall chirality originating exclusively from a stereogenic metal center.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Huazhong University of Science and Technology, School of Materials Science and Engineering, 1037 Luoyu Road, 430074, Wuhan, CHINA.
Organics electrooxidation coupled hydrogen production has attracted increasing attention due to the low operation voltage. Nevertheless, the spontaneous production of hydrogen coupled with organics valorization remains challenging. Herein, we develop ultrathin Au/Pt twin nanowire (NW) catalysts for both electrochemical glucose oxidation and hydrogen evolution reaction towards a spontaneous hydrogen production system.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with asymmetric transition metal catalysis. On one hand, we have rationalized that organometallic compounds can serve as molecular electrocatalysts (mediators) to reduce overpotentials and enhance both the reactivity and selectivity of reactions. On the other hand, the conditions for asymmetric transition metal catalysis can be substantially improved through electrochemistry, enabling precise modulation of the transition metal's oxidation state by controlling electrochemical potentials and regulating the electron transfer rate via current adjustments.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
BioCIS, Faculté de Pharmacie, Université Paris-Saclay, CNRS, Orsay 91400, France.
The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-metal stereoinduction mode could serve as an alternative mechanism for BINOL-metal catalysis, based on mechanistic studies of BINOL-aluminum-catalyzed asymmetric hydroboration of heteroaryl ketones.
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