The acceptorless dehydrogenation reaction is a sustainable and atom-economical methodology in organic synthesis, resulting in the byproducts of only hydrogen or water. Herein, a robust Co-Si/CN catalyst (derived from ZIF@SiO composite) has been synthesized through a one-step assembly process via pyrolysis and etching. This catalyst has been employed for the acceptorless dehydrogenative coupling of 2-aminoalcohols with secondary alcohols, enabling efficient conversion of various substrates into desired quinoline or pyridine derivatives with a yield of up to 94 %.
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http://dx.doi.org/10.1002/chem.202402168 | DOI Listing |
Nat Commun
January 2025
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
The advancement of an effective hydrogen liberation technology from liquid organic hydrogen carriers, particularly cycloalkanes such as cyclohexane and methylcyclohexane, holds significance in realizing a hydrogen-centric society. However, the attainment of homogeneous catalytic acceptorless dehydrogenation characterized by elevated selectivity for thorough aromatization under mild conditions remains unrealized. In this study, a catalyst system, facilitated by a double hydrogen atom transfer processes, has been devised for the catalytic acceptorless dehydrogenation of inert cycloalkanes at ambient temperature under visible light irradiation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Oxford, Department of Chemistry Chemistry Research Laboratory, Mansfield Road, OX1 3TA, Oxford, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Compounds containing quaternary stereocentres are a valuable motif in biologically active compounds. Herein we present our strategy to utilise the hydrogen borrowing manifold to access α-quaternary ketones via a tandem acceptorless dehydrogenation-cyclisation cascade. This new application of the methodology results in the formation of five- and six-membered carbocycles with a high degree of diastereoselectivity.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian 116024, China.
We report the first example of photocatalytic acceptorless dehydrogenation using cationic Eosin Y as a bifunctional photocatalyst, without metal catalysts or HAT reagents. Under Bayesian optimized conditions, a wide range of flavones were synthesized in moderate to excellent yields, many of which were reported with biological activities. Mechanistic studies suggest that flavones likely form through two HAT processes, with hydrogen release occurring photoredox.
View Article and Find Full Text PDFJ Org Chem
January 2025
Centre for Organometallic Chemistry, School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, India.
A streamlined strategy for the one-pot synthesis of isoxazolone analogues has been developed through an acceptorless dehydrogenative annulation (ADA) pathway by employing new Ru(II) hydride complexes as effective catalysts. New Ru(II) complexes () tailored with N̂O chelating carbazolone benzhydrazone ligands were synthesized and their formation was confirmed using analytical and spectral techniques including FT-IR and NMR. The structural configuration of the complexes featuring an octahedral geometry around the Ru(II) ion was precisely determined by single-crystal X-ray diffraction analysis.
View Article and Find Full Text PDFChem Asian J
December 2024
IIT Indore: Indian Institute of Technology Indore, Deptm. of Chemistry, Khandwa Road, Simrol, 453552, Indore, INDIA.
This study presents a highly efficient and cost-effective Cu/CeO2 catalyst for the acceptorless dehydrogenative coupling (ADC) of o-aminobenzyl alcohols and secondary alcohols to synthesize quinolines. The catalyst demonstrated over 90% yield in quinoline production under mild conditions, exhibiting excellent tolerance to various functional groups. The Cu/CeO2 catalyst, synthesized via a co-precipitation method, was thoroughly characterized through various techniques like PXRD, XPS, and AC-STEM.
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