Gold‐Catalyzed 1,2‐/1,2‐Bis‐acetoxy Migration of 1,4‐Bis‐propargyl Acetates: A Mechanistic Study |
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Authors: | Teresa de Haro Prof Dr Enrique Gómez‐Bengoa Dr Riccardo Cribiú Dr Xiaogen Huang Prof Dr Cristina Nevado |
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Institution: | 1. Organic Chemistry Institute, University of Zürich, Winterthurerstrasse 190, 8057 Zürich (Switzerland), Fax: (+41)?44‐6356812;2. Departamento de Química Orgánica I, Universidad del Pais Vasco, Apdo 1072, 20080 Donostia ‐ San Sebastián (Spain) |
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Abstract: | The late transition metal catalyzed rearrangement of propargyl acetates offers an interesting platform for the development of synthetically useful transformations. We have recently shown that gold complexes can catalyze a highly selective tandem 1,2‐/1,2‐bis‐acetoxy migration in 1,4‐bis‐propargyl acetates to form 2,3‐bis‐acetoxy‐1,3‐dienes. In this way, (1Z,3Z)‐ or (1Z,3E)‐ and (1E,3Z)‐1,3‐dienes could be obtained in a stereocontrolled manner depending on the electronic and steric features of the ancillary ligand bound to gold and the substituents at the propargylic positions. In this work, we report an experimental study on the scope of this transformation, plus a detailed theoretical examination of the reaction mechanism, which has revealed the key features responsible for the reaction stereoselectivity. Synthetic applications towards the one‐pot synthesis of quinoxaline heterocycles and tandem Diels–Alder processes have also been devised. |
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Keywords: | gold homogeneous catalysis ligand effects propargyl acetates stereoselectivity |
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