Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Beijing National Laboratory for Molecular Sciences, Beijing, 100190, China.
Angew Chem Int Ed Engl. 2022 Jun 27;61(26):e202200075. doi: 10.1002/anie.202200075. Epub 2022 May 5.
Preparation of skipped dienes with a quaternary carbon center at the C-3 position remains a synthetic challenge. We report here an iridium-catalyzed formal addition of tertiary sp C-H bond to alkyne for the facile preparation of skipped dienes. The tertiary allylic C-H bond is cleaved regioselectively, at the site of which a new C-C bond is formed. Enantioselective construction of acyclic quaternary carbon stereocenters is also demonstrated.
在 C-3 位具有季碳原子中心的缺电子二烯的制备仍然是一个合成挑战。我们在此报告了铱催化的三级 sp³C-H 键与炔烃的加成反应，可用于制备缺电子二烯。三级烯丙基 C-H 键被区域选择性地切断，在该位置形成新的 C-C 键。还证明了非环季碳立体中心的对映选择性构建。
