Lanzi Matteo, Santacroce Veronica, Balestri Davide, Marchiò Luciano, Bigi Franca, Maggi Raimondo, Malacria Max, Maestri Giovanni
Università di Parma, Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Parco Area delle Scienze 17/A, 43124, Parma, Italy.
IMEM-CNR, Parco Area delle Scienze 37/A, 43124, Parma, Italy.
Angew Chem Int Ed Engl. 2019 May 13;58(20):6703-6707. doi: 10.1002/anie.201902837. Epub 2019 Apr 8.
A variety of linear dienynes can deliver complex tetracyclic frameworks in the presence of an Ir complex and visible light. Product formation involves the generation of four new C-C bonds and six contiguous stereocenters, which decorate two [3.1.0] bicyclic units tethered through their bridging quaternary carbon atoms. The internal alkyne acts as a formal dicarbenoid for the generation of two cyclopropanes in these radical cation cascades. This behavior has not been previously observed for organic reactive intermediates and can be extended to intermolecular reactions and diendiynes.
在铱配合物和可见光存在的情况下，多种线性二烯炔可以构建复杂的四环骨架。产物的形成涉及四个新碳-碳键和六个相邻立体中心的产生，这些立体中心修饰了两个通过桥连季碳原子相连的[3.1.0]双环单元。在这些自由基阳离子级联反应中，内部炔烃作为一种形式上的双碳烯体用于生成两个环丙烷。这种行为以前在有机反应中间体中尚未观察到，并且可以扩展到分子间反应和二烯炔。
