A new light-driven asymmetric ion-pair catalysis procedure for the metal-free enantioselective hydrogenation of in situ generated pyrylium ions from readily available chalcones was developed (see scheme). The photo-assisted Brønsted acid catalyzed procedure has broad scope and allows, for the first time, access to valuable 4H-chromenes in good yields and with excellent enantioselectivities.
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http://dx.doi.org/10.1002/chem.201300766 | DOI Listing |
Chemistry
December 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.
A synergistic Pd/Cu catalyst system has been developed for stereodivergent transformation of Morita-Baylis-Hillman (MBH) carbonates and Schiff bases derived from simple amino acids to afford a series of optically active β-branched γ-methyleneglutamic acid derivatives with adjacent tertiary/tertiary and quaternary/tertiary stereocenters in high yields (up to 96 %) with excellent diastereo- and enantioselectivities (>20/1 dr and >99 % ee in most cases) under mild conditions. The use of SKP ligand is disclosed to be crucial for the success of the transformation, and in particular allowing the reaction to proceed at low catalyst loading (0.02 mol % for Pd and 0.
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November 2024
Nelson Mandela University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth, 6031, South Africa.
The solvated title compound, (CHP)[CoCl(CHP)]·2CH, is the tri-phenyl-phospho-nium salt of an anionic Co chlorido coordination compound; the asymmetric unit features an ion-pair and two benzene solvent molecules. One of the solvent mol-ecules shows rotational disorder. C-H⋯Cl and P-H⋯Cl contacts connect the individual constituents into infinite chains extending parallel to [010].
View Article and Find Full Text PDFJ Org Chem
October 2024
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
On the basis of the chiral ion pair between catalytic anionic stereogenic-at-cobalt(III) complexes and halonium ion intermediates, an asymmetric halogenation/semipinacol rearrangement reaction has been established using -bromosuccinimide as the halogen source. This protocol provides an alternative approach for accessing a diverse set of chiral β-bromocycloketones in good yields with high enantioselectivities (≤96% yield, 95.5:4.
View Article and Find Full Text PDFNat Commun
August 2024
College of Pharmaceutical Science & Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou, P. R. China.
N-oxides play a pivotal role in natural products and emerging drug design, while also serving as valuable ligand scaffolds in organometallic chemistry. Among heteroatom oxidations, the conversion of amines to N-oxides is a critical and challenging facet. We present here a highly enantioselective N-oxidation methodology for both cyclic and acyclic amines.
View Article and Find Full Text PDFSmall
November 2024
Research Institute for Sustainable Energy, Center for Research and Education in Science and Technology (TCG-CREST), Salt Lake, Kolkata, 700091, India.
Application of an aqueous Zn-ion battery is plagued by a water-induced hydrogen evolution reaction (HER), resulting in local pH variations and an unstable electrode-electrolyte interface (EEI) with uncontrolled Zn plating and side reactions. Here, 4-methyl pyridine N-oxide (PNO) is introduced as a redox non-innocent additive that comprises a hydrophilic bipolar N-O ion pair as a coordinating ligand for Zn and a hydrophobic ─CH group at the para position of the pyridine ring that reduces water activity at the EEI, thereby enhancing stability. The N-O moiety of PNO possesses the unique functionality of an efficient push electron donor and pull electron acceptor, thus maintaining the desired pH during charging/discharging.
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