Direct Allylic C(sp3)−H and Vinylic C(sp2)−H Thiolation with Hydrogen Evolution by Quantum Dots and Visible Light
Authors:
- 4 March 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 60 (21) , 11779-11783
Abstract
Direct allylic C−H thiolation is straightforward for allylic C(sp3)−S bond formation. However, strong interactions between thiol and transition metal catalysts lead to deactivation of the catalytic cycle or oxidation of sulfur atom under oxidative condition. Thus, direct allylic C(sp3)−H thiolation has proved difficult. Represented herein is an exceptional for direct, efficient, atom‐ and step‐economic thiolation of allylic C(sp3)−H and thiol S−H under visible light irradiation. Radical trapping experiments and electron paramagnetic resonance (EPR) spectroscopy identified the allylic radical and thiyl radical generated on the surface of photocatalyst quantum dots (QDs). The C−S bond formation does not require external oxidants and radical initiators, and hydrogen (H2) is produced as byproduct. When vinylic C(sp2)−H was used instead of allylic C(sp3)−H bond, the radical‐radical cross‐coupling of C(sp2)−H and S−H was achieved with liberation of H2. Such a unique transformation opens up a door toward direct C−H and S−H coupling for valuable organosulfur chemistry.Keywords
Funding Information
- National Natural Science Foundation of China (22088102, 21933007 and 21861132004)
- K. C. Wong Education Foundation
This publication has 66 references indexed in Scilit:
- Allyl Sulfides Inhibit Cell Growth of Skin Cancer Cells through Induction of DNA Damage Mediated G2/M Arrest and ApoptosisJournal of Agricultural and Food Chemistry, 2010
- Catalytic Intermolecular Allylic C—H AlkylationJournal of the American Chemical Society, 2008
- Allyl Sulfides Are Privileged Substrates in Aqueous Cross-Metathesis: Application to Site-Selective Protein ModificationJournal of the American Chemical Society, 2008
- Catalytic Intermolecular Linear Allylic C−H Amination via Heterobimetallic CatalysisJournal of the American Chemical Society, 2008
- Catalytic Allylic Alkylation via the Cross-Dehydrogenative-Coupling Reaction between Allylic sp3C−H and Methylenic sp3C−H BondsJournal of the American Chemical Society, 2005
- Rhodium-Catalyzed Alkyne Hydrothiolation with Aromatic and Aliphatic ThiolsJournal of the American Chemical Society, 2005
- Asymmetric Transition-Metal-Catalyzed Allylic Alkylations: Applications in Total SynthesisChemical Reviews, 2003
- Catalytic Allylic Oxidation of Alkenes Using an Asymmetric Kharasch–Sosnovsky ReactionAngewandte Chemie International Edition, 2001
- Metal-Catalyzed Carbon−Sulfur Bond FormationChemical Reviews, 2000
- First Ruthenium-Catalyzed Allylation of Thiols Enables the General Synthesis of Allylic SulfidesJournal of the American Chemical Society, 1999