A room-temperature C-H bond functionalization of benzamides has been developed by merging a photocatalyst with a cobalt catalyst for the synthesis of isoindolone spirosuccinimides. The reaction proceeds in aerobic conditions and does not require any sacrificial external oxidants such as Ag(I) or Mn(III) salts. Visible light activates the photocatalyst, and it acts as an electron-transfer reagent and helps in the fundamental organometallic steps by modulating the oxidation state of the cobalt complex. This C-H bond functionalization and spirocyclization showed wide substrate scope and good functional group tolerance. A possible reaction mechanism was proposed from the experimental outcome, showing that C-H bond activation is irreversible and not the rate-determining step.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.0c02120 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Homo-Mannich Reaction of Cyclopropanols: A Versatile Tool for Natural Product Synthesis.
Acc Chem Res
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China.
ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to an imine or iminium ion, is one of the most widely used synthetic methods for the synthesis of β-amino carbonyl compounds. Nevertheless, the homo-Mannich reaction, which utilizes a homoenolate intermediate as the nucleophilic partner and provides straightforward access to the valuable γ-amino carbonyl compounds, remains underexplored. This can be largely attributed to the difficulties in generation and manipulation of the homoenolate species, despite various homoenolate equivalents that have been developed.
View Article and Find Full Text PDFTerminal Alkyne Activation by an Al(I)-Centered Anion: Impact on the Mechanism of Alkali Metal Identity.
Organometallics
January 2025
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
The group 1 alumanyls, [{SiN}AlM] (M = K, Rb, Cs; SiN = {CHSiMeNDipp}), display a variable kinetic facility (K < Rb < Cs) toward oxidative addition of the acidic C-H bond of terminal alkynes to provide the corresponding alkali metal hydrido(alkynyl)aluminate derivatives. Theoretical analysis of the formation of these compounds through density functional theory (DFT) calculations implies that the experimentally observed changes in reaction rate are a consequence of the variable stability of the [{SiN}AlM] dimers, the integrity of which reflects the ability of M to maintain the polyhapto group 1-arene interactions necessary for dimer propagation. These observations highlight that such "on-dimer" reactivity takes place sequentially and also that the ability of each constituent Al(I) center to effect the activation of the organic substrate is kinetically differentiated.
View Article and Find Full Text PDFVisible-Light-Induced Synthesis of Esters via a Self-Propagating Radical Reaction.
J Org Chem
January 2025
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
We herein disclose a visible-light-induced synthesis of aryl esters through the cross-dehydrogenative coupling of aldehydes with phenols using BrCCl, in which phenolate functions as both a substrate and a photosensitizer. This transition-metal- and photocatalyst-free visible-light-induced esterification is suitable for a wide range of substrates and gives moderate to excellent yields (up to 95%). Mechanistic studies provided evidence of a self-propagating radical reaction involving homolytic cleavage of the aldehydic C-H bond and the formation of acyl bromides.
View Article and Find Full Text PDFRh(III)-Catalyzed [4 + 2] Annulation and Dehydrogenative Annulation of -Chloroimines with Maleimides.
J Org Chem
January 2025
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China.
We herein report a Rh(III)-catalyzed C-H bond coupling of -chloroimines with maleimides, in which the [4 + 2] annulation and dehydrogenative annulation processes can be selectively achieved by simply adjusting the reaction conditions. This protocol is compatible with various functional groups, shows exquisite selectivity, and presents a concise synthetic procedure to respective products in moderate to good yields. With all these merits, this strategy may be applicable in the construction of related azaheterocyclic skeletons.
View Article and Find Full Text PDFSynthesis and Reactivity of a Non-Heme μ-Oxodicobalt(IV) Complex.
Chemistry
January 2025
Indian Institute of Technology Delhi, Department of Chemistry, Hauz Khas, 110016, New Delhi, INDIA.
A mononuclear CoIII complex (1) of a bisamide-bisalkoxide donor ligand was synthesized and thoroughly characterized. The reaction of 1 with 0.5 equiv.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!