Catalytic, stereoselective N-heterocyclic carbene-catalyzed reactions facilitate efficient construction of many different heterocyclic compounds, such as the enantioenriched 5-membered (γ) lactones highlighted in this tutorial review. Herein, various strategies to enable formal [3+2] type annulations between electrophilic carbonyl equivalents and homoenolate nucleophiles for the synthesis of γ-lactones are summarized.
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http://dx.doi.org/10.1039/c7cs00386b | DOI Listing |
Beilstein J Org Chem
January 2025
Department of Organic Chemistry, Faculty of Natural Science, Comenius University Bratislava, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia.
Axial chirality is present in a variety of naturally occurring compounds, and is becoming increasingly relevant also in medicine. Many axially chiral compounds are important as catalysts in asymmetric catalysis or have chiroptical properties. This review overviews recent progress in the synthesis of axially chiral compounds via asymmetric organocatalysis.
View Article and Find Full Text PDFNat Commun
January 2025
School of Chemistry, Chemical Engineering, and Biotechnology, Nanyang Technological University, Singapore, 637371, Singapore.
Acylation stands as a fundamental process in both biological pathways and synthetic chemical reactions, with acylated saccharides and their derivatives holding diverse applications ranging from bioactive agents to synthetic building blocks. A longstanding objective in organic synthesis has been the site-selective acylation of saccharides without extensive pre-protection of alcohol units. In this study, we demonstrate that by simply altering the chirality of N-heterocyclic carbene (NHC) organic catalysts, the site-selectivity of saccharide acylation reactions can be effectively modulated.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants.
View Article and Find Full Text PDFJ Org Chem
December 2024
Anhui Province Key Laboratory of Value-Added Catalytic Conversion and Reaction Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, China.
An innovative solution that overcomes the long-standing inherently low efficiency in -heterocyclic carbene-catalyzed aerobic oxidation of aldehydes is reported. This solution included the design and synthesis of a novel polymerized catalyst and the utilization of a flow reactor. The unprecedentedly high efficiency achieved via this protocol makes it synthetically applicable.
View Article and Find Full Text PDFChem Sci
December 2024
Key Laboratory of Advanced Light Conversion Materials and Biophotonics School of Chemistry and Life Resources, Renmin University of China Beijing 100872 China
Cyclopropanes are ubiquitous and key structural motifs in commercially available drugs and bioactive molecules. Herein, we present regio-selective acylation of aryl cyclopropanes with cooperative photoredox and N-heterocyclic carbene catalysis. This approach involves a deconstruction-reconstruction strategy γ-chloro-ketones as intermediates and fulfills the formal C(sp)-H functionalization of cyclopropanes.
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