Visible‐Light‐Promoted Polycyclizations of Dienynes. (8th April 2019)

• Record Type: Journal Article
• Authors: Lanzi, Matteo; Santacroce, Veronica; Balestri, Davide; Marchiò, Luciano; Bigi, Franca; Maggi, Raimondo; Malacria, Max; Maestri, Giovanni
• Is Part Of: Angewandte Chemie. Volume 131:Number 20(2019)
• Page Start: 6775
• Page End: 6779
• Publication Date: 2019-04-08
• Subjects: Carbenoide -- Dominoreaktionen -- Photokatalyse -- Radikalkationen -- Sichtbares Licht; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201902837
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A variety of linear dienynes can deliver complex tetracyclic frameworks in the presence of an Ir III 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. Abstract : Carbenoide im Rampenlicht : Sichtbares Licht und ein Iridium‐Komplex ermöglichen die Tetracyclisierung linearer Dienine über eine Radikalkationenkaskade mit Carbenoid‐Intermediaten. Bei der Produktbildung entstehen vier neue C‐C‐Bindungen und sechs benachbarte Stereozentren an zwei [3.1.0]Bicyclen, die über quartäre Kohlenstoffzentren verbrückt sind.