Abstract
Thioesters play important roles in chemistry and biology, but their synthesis generally exhibits a poor atom economy and generates copious waste. We report here the dehydrogenative coupling of alcohols and thiols to yield thioesters and evolve H-2. This waste-free reaction is catalysed by an acridine-based ruthenium pincer complex in hexamethyldisiloxane as the optimal solvent without any additives. Various thioesters were formed in good-to-excellent yields using equivalent amounts of alcohols and thiols in excellent selectivity with hydrogen gas as the only by-product. A plausible mechanism, which involves an outer-sphere dehydrogenation process in which the thiol not only serves as a reactant, but also as an assisting ligand, is proposed based on mechanistic studies and the isolation of intermediates. This system provides a facile, efficient and waste-free synthesis of thioesters.
| Original language | English |
|---|---|
| Pages (from-to) | 887-892 |
| Number of pages | 6 |
| Journal | Nature Catalysis |
| Volume | 3 |
| Issue number | 11 |
| Early online date | 28 Sept 2020 |
| DOIs | |
| Publication status | Published - Nov 2020 |
Funding
This research was supported by the European Research Council (ERC AdG 692775). We thank S. Semenov for his help during the project. M.R. acknowledges the Zuckerman STEM Leadership Program for a research fellowship. D.M. is the Israel Matz Professorial Chair of Organic Chemistry. Author contributions - D.M. conceived and directed the project. J.L. and D.M. designed the experiments. J.L. performed and analysed the experiments. M.R. performed the computational studies. L.A., Y.D.-P. and G.S. provided helpful discussions towards NMR spectroscopy, X-ray structure determination and high-resolution mass spectrometry of the Ru complexes, respectively. Y.B.-D. prepared the ligands. J.L. and D.M. prepared the manuscript.
All Science Journal Classification (ASJC) codes
- Catalysis
- Bioengineering
- Biochemistry
- Process Chemistry and Technology