We report a transition metal-free approach for the regioselective functionalization of benzylic C(sp)-H bonds using alcohols and carboxylic acids as the nucleophiles. This straightforward and general route has provided various benzylic ethers and esters, including twelve pharmaceutically relevant compounds.
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http://dx.doi.org/10.1039/d2cc02661a | DOI Listing |
Synthesis of complex, multiring, spirocyclic, 1,3-dicarbonyl fused, and highly functionalized 5-phenyl-1-azabicyclo[3.1.0]hexanes (ABCH) has been achieved by an intermolecular reaction of 2-(2'-ketoalkyl)-1,3-indandiones or α,γ-diketo esters with (1-azidovinyl)benzenes under transition metal-free conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Instytut Chemii Organicznej PAN: Instytut Chemii Organicznej Polskiej Akademii Nauk, Institute of Organic Chemistry, Kasprzaka 44/52, 01-224, Warsaw, POLAND.
The development of straightforward synthetic methods for photoactive polycyclic aromatic hydrocarbons (PAHs) that avoid Pd-catalyzed or radical-based processes remains a challenge. Such methods are essential to reducing the cost and environmental impact of organic photodevices. In this work, we present a one-pot synthetic approach for creating novel bipolar PAHs with extended π-conjugation, which are not accessible via conventional Pd-catalyzed routes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Institute of Materials Research and Engineering, Sensor and Flexible Electronics, 2 Fusionopolis Way, 138634, SINGAPORE.
Radical covalent organic frameworks (RCOFs) have demonstrated significant potential in redox catalysis and energy conversion applications. However, the synthesis of stable RCOFs with well-defined neutral carbon radical centers is challenging due to the inherent radical instability, limited synthetic methods and characterization difficulties. Building upon the understanding of stable carbon radicals and structural modulations for preparing crystalline COFs, herein we report the synthesis of a crystalline carbon-centered RCOF through a facile post-oxidation process.
View Article and Find Full Text PDFChem Rev
January 2025
Department of Chemistry, Northeast Normal University, Changchun 130024, China.
-Sulfonyl hydrazones have been extensively used as operationally safe carbene precursors in modern organic synthesis due to their ready availability, facile functionalization, and environmental benignity. Over the past two decades, there has been tremendous progress in the carbene chemistry of -sulfonyl hydrazones in the presence of transition metal catalysts, under metal-free conditions, or using photocatalysts under photoirradiation conditions. Many carbene transfer reactions of -sulfonyl hydrazones are unique and cannot be achieved by any alternative methods.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Department of Catalysis & Fine Chemicals, CSIR- Indian Institute of Chemical Technology, Uppal Road, Hyderabad, Telangana State 500007, India.
Photoassisted CO reduction employing a metal-free system is both challenging and fascinating. In our study, we present a structural engineering strategy to tune the potential energy barrier, which, in turn, affects the photoreduction ability. A series of porphyrin-based porous organic polymers () were hydrothermally synthesized and the influence of keto-enol tautomerization on the CO photoreduction potential has been rigorously investigated.
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