Catalyst-controlled functionalization of unmodified carbonyl compounds is a relevant operation in organic synthesis, especially when high levels of site- and stereoselectivity can be attained. This objective is now within reach for some subsets of enolizable substrates using various types of activation mechanisms. Recent contributions to this area include enantioselective transformations that proceed via transiently generated noncovalent di(tri)enolate-catalyst coordination species. While relatively easier to form than simple enolate congeners, di(tri)enolates are ambifunctional in nature and so control of the reaction regioselectivity becomes an issue. This Minireview discusses in some detail this and other problems, and how noncovalent activation approaches based on metallic and metal free catalysts have been developed to advance the field.
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http://dx.doi.org/10.1002/chem.202100756 | DOI Listing |
An unprecedented divergent aromatization reaction of α-halobenzyl γ-butenolides has been described for the selective and concise synthesis of highly substituted benzo and higher π-extended fluorenones, and 1,3-disubstituted naphthalenes depending on the migration ability of the quaternary α-substituent. This aromatization switch from Ag-mediated planarization to ylidenebutenolides likely originates from selective protonation on the enolic double bond rather than the benzyl halides by TfOH.
View Article and Find Full Text PDFJ Org Chem
July 2024
Samara State Technical University, 244 Molodogvardeyskaya St., Samara 443100, Russian Federation.
Various substituted pyrrolo[1,2-]quinolines and pyrrolo[2,1-]isoquinolines were synthesized in good to high yields by the EtN-mediated reaction of push-pull 3-nitrobenzofurans or 1-Ts-/1-Ms-3-nitroindoles and precursors of carbonyl-stabilized quinolinium and isoquinolinium ylides as 1,3-dipole equivalents. These transformations proceed in a one-pot manner starting with the formal [3 + 2]-cycloaddition stage, which is accompanied by double dearomatization of both quinoline/isoquinoline and benzofuran/indole moieties, followed by ring-opening of cyclic intermediate formed and nitrous acid elimination sequence. [3 + 2]-Cycloadducts were isolated as the final products in cases of impossibility or difficulty of their enolization.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2024
Advanced Energy Storage Technology Research Center, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China.
Organics are gaining significance as electrode materials due to their merits of multi-electron reaction sites, flexible rearrangeable structures and redox reversibility. However, organics encounter finite electronic conductivity and inferior durability especially in organic electrolytes. To circumvent above barriers, we propose a novel design strategy, constructing conductive network structures with extended π-π superposition effect by manipulating intermolecular interaction.
View Article and Find Full Text PDFJACS Au
December 2023
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
Photoexcitation of keto-enamine allows intramolecular proton transfer from C-NH to C=O, leading to tautomerization, while the photogenerated isomers are excluded from the study of photocatalytic applications. Herein, we demonstrate the photoisomerization of keto-enamine linkages on covalent organic frameworks (COFs) induced by excited-state intramolecular proton transfer (ESIPT). Partial enolization generates partially enolized photoisomers with a mixture of keto (C=O) and enol (OH) forms, conferring extended π-conjugation with an increase in electron density.
View Article and Find Full Text PDFChemistry
March 2024
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, Assam, India, 781039.
C-C bond forming reaction of ketone with aldehyde is well-studied for the synthesis of α, β-unsaturated ketones, however, the reaction with two different ketones to unsaturated carbonyl compound has not yet been systematically studied. Probably due to the relatively low reactivity of ketones as electrophiles (aldol acceptors), its propensity for retro-aldol reaction. The reactions often suffer from unsatisfactory chemoselectivity (self- vs.
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