Mechanistic Studies on the Rearrangement of 1‐Alkenyl‐2‐alkynylcyclopropanes: From Allylic Gold(I) Cations to Stable Carbocations1. Issue 45 (15th September 2014)

• Record Type: Journal Article
• Authors: Tudela, Eva; González, Jairo; Vicente, Rubén; Santamaría, Javier; Rodríguez, Miguel A.; Ballesteros, Alfredo
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 45(2014)
• Page Start: 12097
• Page End: 12100
• Publication Date: 2014-09-15
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201407055
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>An allylic gold(I) cation, proposed as key intermediate in the gold‐promoted rearrangement of 1, 5‐enynes bearing a fixed conformation, has been detected and characterized by NMR spectroscopy. Moreover, its participation in the overall transformation was confirmed. Computational studies indicate that the gold‐catalyzed transformation occurs through an uncommon rearrangement. Additionally, this study led us to isolate and characterize a stable homoantiaromatic carbocation.</p> </abstract>