Divergent Gold(I)‐Catalyzed Skeletal Rearrangements of 1,7‐Enynes |
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Authors: | Rebecca Meiß Dr Kamal Kumar Prof?Dr Herbert Waldmann |
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Institution: | 1. Max‐Planck‐Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto‐Hahn‐Stra?e 11, 44227 Dortmund (Germany);2. Technische Universit?t Dortmund, Fakult?t Chemie, Chemische Biologie, Otto‐Hahn‐Stra?e 6, 44221 Dortmund (Germany) |
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Abstract: | The gold(I) complex catalyzed cycloisomerization and skeletal rearrangement of 1,n‐enynes (n=5–7) is a powerful methodology for the efficient synthesis of complex molecular architectures. In contrast to 1,6‐enynes, readily accessible homologous 1,7‐enynes are largely unexplored in such transformations. Here, the divergent skeletal rearrangement of all‐carbon 1,7‐enynes by catalysis with a cationic gold(I) complex is reported. Depending on electronic and steric factors, differently substituted 1,7‐enynes react via different carbocations formed from a common gold carbene intermediate to yield on the one hand novel exocyclic allenes and on the other hand tricyclic hexahydro‐anthracenes through a novel dehydrogenative Diels–Alder reaction. |
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Keywords: | catalysis enynes gold synthesis design synthetic methods |
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