Sulfur in Waste-Free Sustainable Synthesis: Advancing Carbon-Carbon Coupling Techniques.

This review explores the pivotal role of sulfur in advancing sustainable carbon-carbon (C-C) coupling reactions. The unique electronic properties of sulfur, as a soft Lewis base with significant mesomeric effect make it an excellent candidate for initiating radical transformations, directing C-H-activation, and facilitating cycloaddition and C-S bond dissociation reactions. These attributes are crucial for developing waste-free methodologies in green chemistry. Our mini-review is focused on existing sulfur-directed C-C coupling techniques, emphasizing their sustainability and comparing state-of-the-art methods with traditional approaches. The review highlights the importance of this research in addressing current challenges in organic synthesis and catalysis. The innovative use of sulfur in photocatalytic, electrochemical and metal-catalyzed processes not only exemplifies significant advancements in the field but also opens new avenues for environmentally friendly chemical processes. By focusing on atom economy and waste minimization, the analysis provides broad appeal and potential for future developments in sustainable organic chemistry.

Reversible Radical Addition Guides Selective Photocatalytic Intermolecular Thiol-Yne-Ene Molecular Assembly.

In modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing the critical issue of controlling selectivity in such complex processes. We introduce a novel approach that revolves around the reversible addition of thiyl radicals to multiple bonds, reshaping the landscape of multicomponent radical reactions. The key to selectivity lies in the intricate interplay between reversibility and the energy landscapes governing C-C bond formation in thiol-yne-ene reactions. The developed approach not only allows to prioritize the thiol-yne-ene cascade, dominating over alternative reactions, but also extends the scope of coupling products obtained from alkenes and alkynes of various structures and electron density distributions, regardless of their relative polarity difference, opening doors to more versatile synthetic possibilities. In the present study, we provide a powerful tool for atom-economical C-S and C-C bond formation, paving the way for the efficient synthesis of complex molecules. Carrying out our experimental and computational studies, we elucidated the fundamental mechanisms underlying radical cascades, a knowledge that can be broadly applied in the field of organic chemistry.

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 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.

Exploring metallic and plastic 3D printed photochemical reactors for customizing chemical synthesis.

Visible light photocatalysis is a rapidly developing branch of chemical synthesis with outstanding sustainable potential and improved reaction design. However, the challenge is that many particular chemical reactions may require dedicated tuned photoreactors to achieve maximal efficiency. This is a critical stumbling block unless the possibility for reactor design becomes available directly in the laboratories. In this work, customized laboratory photoreactors were developed with temperature stabilization and the ability to adapt different LED light sources of various wavelengths. We explore two important concepts for the design of photoreactors: reactors for performing multiple parallel experiments and reactors suitable for scale-up synthesis, allowing a rapid increase in the product amount. Reactors of the first type were efficiently made of metal using metal laser sintering, and reactors of the second type were successfully manufactured from plastic using fused filament fabrication. Practical evaluation has shown good accuracy of the temperature stabilization in the range typically required for organic synthesis for both types of reactors. Synthetic application of 3D printed reactors has shown good utility in test reactions-furan C-H arylation and thiol-yne coupling. The critical effect of temperature stabilization was established for the furan arylation reaction: heating of the reaction mixture may lead to the total vanishing of photochemical effect.