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Divergent Gold(I)‐Catalyzed Skeletal Rearrangements of 1,7‐Enynes
Author(s) -
Meiß Rebecca,
Kumar Kamal,
Waldmann Herbert
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502843
Subject(s) - cycloisomerization , steric effects , carbocation , cationic polymerization , catalysis , chemistry , carbene , yield (engineering) , stereochemistry , combinatorial chemistry , medicinal chemistry , organic chemistry , materials science , metallurgy
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.