Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

The first example of an intermolecular thiol–yne–ene coupling reaction is reported for the one‐pot construction of C−S and C−C bonds. Thiol–yne–ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatal...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-04, Vol.61 (17), p.e202116888-n/a
Main Authors: Burykina, Julia V., Kobelev, Andrey D., Shlapakov, Nikita S., Kostyukovich, Alexander Yu, Fakhrutdinov, Artem N., König, Burkhard, Ananikov, Valentine P.
Format: Article
Language:English
Subjects:
Computer applications
Construction
Coupling (molecular)
Dienes
Hydrogen atoms
Multicomponent Reactions
Photocatalysis
Reaction Mechanisms
Reducing agents
Selectivity
Spectroscopy
Thiol–Yne–Ene
Visible Light
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Summary:The first example of an intermolecular thiol–yne–ene coupling reaction is reported for the one‐pot construction of C−S and C−C bonds. Thiol–yne–ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via C−S three‐electron σ‐bond formation). Investigation of the reaction mechanism by combining online ESI‐UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern–Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical‐involving stages. As a result, previously unavailable products of the thiol–yne–ene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3‐dienes. An atom‐economical metal‐free photoredox three‐component coupling of thiols with readily available alkynes and α‐vinylsulfide has been developed. The reaction uses the easy‐to‐handle EosinY/DBU photocatalytic system, resulting in a one‐pot synthesis of C−S and C−C bonds. The reaction mechanism was investigated by combining mass spectrometry, EPR spectroscopy, isotope labeling, cyclic voltammetry, Stern–Volmer measurements and computational modeling, revealing a unique photoredox cycle.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202116888