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

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

Journal

Angewandte Chemie International Edition
ISSN: 1433-7851 , E-ISSN: 1521-3773

Output data

Year: 2022, Volume: 61, Number: 17, Article number : e202116888, Pages count : DOI: 10.1002/anie.202116888

Authors

Burykina Julia V. ¹ , Kobelev Andrey D. ^2,1 , Shlapakov Nikita S. ^3,1 , Kostyukovich Alexander Yu. ¹ , Fakhrutdinov Artem N. ¹ , König Burkhard ³ , Ananikov Valentine P. ^2,1

Affiliations

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, Moscow, 119991, Russia.
2	Lomonosov Moscow State University, Leninskie Gory GSP-1, 1-3, Moscow, 119991, Russia.
3	Institut für Organische Chemie, Universität Regensburg, Universitätstrasse 31, 93053, Regensburg, Germany.

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.

Burykina J.V. , Kobelev A.D. , Shlapakov N.S. , Kostyukovich A.Y. , Fakhrutdinov A.N. , König B. , Ananikov V.P.
Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction
Angewandte Chemie International Edition. 2022. V.61. N17. e202116888 . DOI: 10.1002/anie.202116888 WOS Scopus OpenAlex

≡ Web of science:	WOS:000763248700001
≡ Scopus:	2-s2.0-85125525239
≡ OpenAlex:	W4220712111