The Nazarov reaction (cyclization) is one of the most useful synthetic tools for the stereoselective preparation of various cyclopentenone scaffolds. This review summarizes recent applications of this reaction to the synthesis of natural compounds and their usefulness to pharmacology analogs published over 2005-2016. Modern protocols for the facile generation of key cationic intermediates and efficient catalytic, in particular asymmetric, versions of Nazarov cyclization are considered. Available literature data are for the first time classified according to the chemical structures of the products, which include relatively simple non-annulated functionalized cyclopentenoids and complex polynuclear cyclopentenone derivatives annulated with one or more non-aromatic, aromatic or heteroaromatic rings. This classification is convenient for specialists in organic synthesis and for researchers working in the area of medicinal and biomolecular chemistry.
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http://dx.doi.org/10.1039/c7ob01981e | DOI Listing |
Int J Mol Sci
January 2025
Research Institute of Chemistry, Peoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia.
In this study, we report the first example of acyclic (amino)(N-pyridinium)carbenoid gold(III) complexes synthesized via a coupling reaction between 2-pyridylselenyl chloride and Au(I)-bound isonitriles. The reaction involves an initial oxidative addition of the Se-Cl moiety to Au(I), followed by the nucleophilic addition of the pyridine fragment to the isonitrile's C≡N bond, furnishing a metallacycle. Importantly, this is the first example of the pyridine acting as a nucleophile towards metal-bound isonitriles.
View Article and Find Full Text PDFNat Commun
December 2024
Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry & Pharmacy, Northwest A&F University, Yangling, Shaanxi, 712100, China.
Marine cyclopianes are a family of diterpenoid with novel carbon skeleton and diverse biological activities. Herein, we report our synthetic and chemical proteomics studies of cyclopiane diterpenes which culminate in the asymmetric total synthesis of conidiogenones C, K and 12β-hydroxy conidiogenone C, and identification of Immunity-related GTPase family M protein 1 (IRGM1) as a cellular target. Our asymmetric synthesis commences from Wieland-Miescher ketone and features a sequential intramolecular Pauson-Khand reaction and gold-catalyzed Nazarov cyclization to rapidly construct the 6-5-5-5 tetracyclic skeleton.
View Article and Find Full Text PDFNanomaterials (Basel)
November 2024
Department of Orthopaedics and Rehabilitation Medicine, Tufts University School of Medicine, Boston, MA 02111, USA.
3D-printed microporous titanium scaffolds enjoy good biointegration with the residuum's soft and bone tissues, and they promote excellent biomechanical properties in attached prostheses. Implant-associated infection, however, remains a major clinical challenge. Silver-based implant coatings can potentially reduce bacterial growth and inhibit biofilm formation, thereby reducing the risk of periprosthetic infections.
View Article and Find Full Text PDFEuropean J Org Chem
November 2024
Department of Chemistry, University of Rochester, Rochester, NY 14627.
This manuscript describes a study of diverse reaction outcomes that stem from the ionization of -alkynyl-Prins adducts. Experimental results have demonstrated unexpected behavior in the nitrogen-containing systems compared to the analogous oxygen derivatives derived from -Prins/-Nazarov sequences. In-depth experimental studies and computational analysis revealed an intricate mechanism involving competing -Nazarov and -Nazarov pathways.
View Article and Find Full Text PDFOrg Lett
December 2024
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200050, China.
We report herein the enantioselective photoinduced Nazarov reaction using a relay strategy of an electrocyclization, followed by parallel kinetic resolution (PKR). No enantioselectivity was observed during electrocyclization due to weak coordination between chiral ligands and the substrate's carbonyl group. However, PKR was successfully achieved in the deprotonation step with a bifunctional chiral thiourea ligand.
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