Hydrogenative Cyclopropanation and Hydrogenative Metathesis. Issue 26 (17th May 2019)

• Record Type: Journal Article
• Authors: Peil, Sebastian; Guthertz, Alexandre; Biberger, Tobias; Fürstner, Alois
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 26(2019)
• Page Start: 8851
• Page End: 8856
• Publication Date: 2019-05-17
• Subjects: carbene complexes -- cyclopropanation -- enynes -- hydrogenation -- metathesis -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201904256
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The unusual geminal hydrogenation of a propargyl alcohol derivative with [Cp X RuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution pattern of the alkene trap. Abstract : Janus character : gem ‐Hydrogenation of propargyl alcohol derivatives provides a conceptually novel entry into metal carbene complexes. Specifically, the use of [Cp*RuCl]4 as catalyst affords pianostool ruthenium carbenes that engage in either cyclopropanation or metathetic ring closure; the outcome of the reaction is largely dictated by the substitution pattern of the chosen olefinic trap.