First experimental example of associative electron upconversion in organic synthesis

The processes of carbon-sulfur bond formation catalyzed by transition metals have been actively studied in recent decades. Many homogeneous and heterogeneous catalytic systems have been developed for the addition of thiols to alkynes; however, there is still a need to create a versatile and selective catalytic method for the synthesis of vinyl sulfides with Markovnikov and anti-Markovnikov selectivity. Recently, the transformations proceeding under the action of visible light are increasingly used in organic synthesis due to their environmental friendliness and efficiency.

In a joint international project with the participation of researchers from ZIOC RAS under the guidance of Academician V.P. Ananikov developed a selective method for the preparation of Markovnikov vinyl sulfides from thiols and alkynes under visible light irradiation. The key advantage of the developed system is simple and available reaction conditions, which makes it possible to reproduce it in any laboratory. Using quantum-chemical calculations and high-resolution mass spectrometry, a mechanism was proposed for the discovered process. This work is the first to propose the control of the selectivity of the reaction with the associative electron upconversion induced by visible light.

Quantum-chemical modeling of parallel reaction paths (picture from the manuscript [doi: 10.1039/D0SC01939A], (C) The Royal Society of Chemistry, CC-BY-NC license)

Source:

Julia V. Burykina, Nikita S. Shlapakov, Evgeniy G. Gordeev, Burkhard König, and Valentine P. Ananikov Selectivity control in thiol–yne click reactions via visible light induced associative electron upconversion Chem. Sci., 2020, 11, 10061-10070, Advance Article, DOI: 10.1039/D0SC01939A.