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Asymmetric metal/organo relay catalysis, utilizing a metal complex and a chiral organocatalyst in a one-pot cascade reaction, is aimed to sequentially impart activation on multiple steps by distinct catalysts. Such a catalysis merges the advantages of both metal catalysis and organocatalysis, providing step-economy, and, more importantly, the potential to achieve inaccessible reactivity by a single catalyst. Chiral phosphoric acids are among the most robust organocatalysts, rendering a broad range of enantioselective bond-forming reactions. The combination of metal complexes and chiral phosphoric acids in a single vessel has been well documented. In particular, the asymmetric relay catalysis of metal complex with chiral phosphoric acid has grown rapidly since 2008. Several excellent reviews have been published to cover almost all examples in this area from 2008 to early 2014; therefore, in this chapter, we will mainly highlight progress from 2014 to mid-2019.
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http://dx.doi.org/10.1007/s41061-019-0263-2 | DOI Listing |
J Org Chem
September 2025
Key Laboratory of Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission & Ministry of Education, School of Ethnic Medicine, Yunnan Minzu University, Kunming 650500, China.
Herein, we describe an enantioselective 1,4-addition of benzofuran-derived azadienes with indolizines under the catalysis of chiral phosphoric acid, which afforded new enantioenriched triarylmethane products in generally good yields (up to 90%) with high enantioselectivities (up to 98% ee). This method enabled the precise synthesis of enantioenriched triarylmethane products, which are notable for their intricate structures and the presence of two (hetero)aryls.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Department of Chemical Biology, Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, Fujian, China.
Minerals have long been recognized for their role in promoting molecular self-assembly in prebiotic environments by serving as insoluble inorganic scaffolds. However, it remains unclear whether soluble inorganic scaffold molecules, such as polyphosphates, also possess the ability to drive the assembly of small molecules. In this study, carbonyldiimidazole (CDI) was used as a chemical activator in combination with polyphosphates (polyP) to investigate the polymerization behavior of the alkaline amino acid arginine (Arg, R).
View Article and Find Full Text PDFChem Asian J
August 2025
Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, 2-24-16, Naka-cho, Koganei, Tokyo, 184-8588, Japan.
Rasagiline mesylate is a monoamine oxidase B inhibitor used clinically for treating Parkinson's disease. Conventional synthesis relies on optical resolution, which limits efficiency and scalability. To overcome these challenges, we developed an enantioselective synthesis route using asymmetric transfer hydrogenation (ATH) of a cyclic propargyl imine intermediate.
View Article and Find Full Text PDFChem Asian J
August 2025
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, Assam, 781039, India.
Herein, we disclose a catalytic asymmetric Friedel-Crafts alkylation of N-aryl anilines with aurone-derived azadienes for the first synthesis of benzofuran and N-aryl aniline containing triarylmethanes. An easily available chiral phosphoric acid, TRIP, was found to be effective for this reaction. The triarylmethanes with benzofuran and N-aryl aniline motifs were obtained in moderate yields with high regio- and good to high enantioselectivities.
View Article and Find Full Text PDFNat Mater
September 2025
National Key Laboratory of Advanced Micro and Nano Manufacture Technology, Department of Micro/Nano Electronics, School of Integrated Circuits, Shanghai Jiao Tong University, Shanghai, China.
Black phosphorus nanoribbons (BPNRs) with a tunable bandgap and intriguing electronic and optical properties hold strong potential for logic applications. However, efficiently producing high-quality BPNRs with precise control over their size and structure remains a great challenge. Here we achieved high-quality, narrow and clean BPNRs with nearly atomically smooth edges and well-defined edge orientation at high yield (up to ~95%) through the sonochemical exfoliation of the synthesized bulk BP crystals with a slightly enlarged lattice parameter along the armchair direction.
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