Fischer David M, Freis Manuel, Amberg Willi M, Lindner Henry, Carreira Erick M
Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich 8093 Zurich Switzerland
Chem Sci. 2023 Jun 14;14(26):7256-7261. doi: 10.1039/d3sc02250a. eCollection 2023 Jul 5.
We report the difunctionalization of unactivated, terminal olefins through intermolecular addition of α-bromoketones, -esters, and -nitriles followed by formation of 4- to 6-membered heterocycles with pendant nucleophiles. The reaction can be conducted with alcohols, acids, and sulfonamides as nucleophiles furnishing products bearing 1,4 functional group relationships that offer various handles for further manipulation. Salient features of the transformations are the use of 0.5 mol% of a benzothiazinoquinoxaline organophotoredox catalyst and their robustness with respect to air and moisture. Mechanistic investigations are carried out and a catalytic cycle for the reaction is proposed.
我们报道了通过α-溴代酮、酯和腈的分子间加成，随后与侧链亲核试剂形成4至6元杂环，实现未活化末端烯烃的双官能化反应。该反应可以使用醇、酸和磺酰胺作为亲核试剂进行，得到具有1,4官能团关系的产物，为进一步操作提供了多种途径。这些转化反应的显著特点是使用0.5 mol%的苯并噻嗪并喹喔啉有机光氧化还原催化剂，并且它们对空气和水分具有稳定性。我们进行了机理研究并提出了该反应的催化循环。
