Sorribes Iván, Corma Avelino
Instituto de Tecnología Química , Universitat Politecnica de València-Consejo Superior de Investigaciones Científicas , Avenida Los Naranjos s/n , 46022 Valencia , Spain . Email:
Chem Sci. 2019 Feb 4;10(10):3130-3142. doi: 10.1039/c8sc05782f. eCollection 2019 Mar 14.
Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (HS) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
纳米层状硫化钴钼（Co-Mo-S）材料已被确立为构建C-S键的优良催化剂。这些催化剂能够以良好至优异的产率，从结构多样的硫醇以及易得的伯醇和仲醇制备多种硫醚。已证明在双键、腈、羧酸酯和卤素等敏感基团存在下具有化学选择性。还表明该反应通过氢自转移（借氢）机制进行，该机制涉及Co-Mo-S介导的脱氢和氢化反应。利用这些储量丰富的金属基硫化物催化剂，还开发了一种基于醇与硫化氢（HS）硫醚化以提供对称硫醚的新型催化方案。
