Schreib Benedikt S, Fadel Marlene, Carreira Erick M
Laboratorium für Organische Chemie, HCI H335, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2020 May 11;59(20):7818-7822. doi: 10.1002/anie.202000935. Epub 2020 Mar 19.
Palladium-catalyzed regio- and diastereoselective C-H functionalization with bromoalkynes and electronically unbiased olefins is reported. The picolinamide directing group enables the formation of putative 5 and 6-exo-metallacycles as intermediates to afford monoalkynylated products in up to 91 % yield in a stereospecific fashion. The systematic study reveals that substrates with a wide range of substituents on the olefin and bromoalkyne coupling partners are tolerated. Chemoselective transformations were demonstrated for the obtained amides, olefins, and alkynes.
报道了钯催化的溴代炔烃与电子中性烯烃的区域和非对映选择性C-H官能化反应。吡啶甲酰胺导向基团能够形成假定的5-外和6-外金属环作为中间体，以立体专一的方式提供产率高达91%的单炔基化产物。系统研究表明，烯烃和溴代炔烃偶联伙伴上具有广泛取代基的底物均可耐受。对所得酰胺、烯烃和炔烃进行了化学选择性转化。
