Scientists from ZIOC RAS developed an effective and atom-economical approach to highly functionalized vinylsulfides

Vinyl sulfides are widely used in organic chemistry, including free-radical reactions, and are also important structural fragments in medicinal chemistry, polymer chemistry, and materials science. One of the most widespread methods for the preparation of vinyl sulfides is the hydrothiolation of alkynes catalyzed by transition metals. However, regio- and stereoselectivity of this process is often difficult to control.

Researchers from laboratory № 30 of ZIOC RAS succeeded in developing an efficient and atom-economical approach to the hydrothiolation of cyclopropylacetylenes. As a result, highly functionalized vinyl sulfides of the Markovnikov type were obtained. Despite the possibility of a large number of side radical processes involving the starting thiols and the cyclopropane ring, the target products are formed with high selectivity (up to 99: 1) and yields are almost quantitative. Using the molecular dynamics method, the key stage of the process mechanism was studied — the insertion of alkyne into the Pd-S bond. Analysis of electronic properties and comparative advantages of transient structures provides a convincing theoretical justification for the high regioselectivity of the process. The results obtained open up great prospects for their usage in the targeted catalytic functionalization of a wide range of organic substrates.

Source:

Liliya T. Sahharova, Evgeniy G. Gordeev, Dmitry B. Eremin, and Valentine P. Ananikov Pd-Catalyzed Synthesis of Densely Functionalized Cyclopropyl Vinyl Sulfides Reveals the Origin of High Selectivity in a Fundamental Alkyne Insertion Step ACS Catal. 2020, 10, 17, 9872–9888, DOI: 10.1021/acscatal.0c02053.