Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw 01-224, Poland.
Chem Commun (Camb). 2023 May 4;59(37):5547-5550. doi: 10.1039/d3cc00671a.
A cascade of 5- intramolecular nucleophilic addition of enamine to terminal alkyne followed by cross coupling has been demonstrated for the first time. Two new C-C bonds are stereoselectively forged by a single Pd-complex capable of catalyzing two mechanistically diverse transformations. Mechanistic investigations identified cyclization as the rate limiting step relying on the facile displacement of OTf, weakly bound to the Pd-center, by the alkyne.
首次证明了烯胺的 5-分子内亲核加成到末端炔烃，然后进行交叉偶联的级联反应。通过单个钯配合物能够催化两种机理截然不同的转化，立体选择性地形成两个新的 C-C 键。机理研究表明，环化是速率限制步骤，依靠 OTf 易于被炔烃取代，OTf 与钯中心结合较弱。
