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Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes
Author(s) -
GonzálezEsguevillas María,
PascualEscudero Ana,
Adrio Javier,
Carretero Juan C.
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.201500182
Subject(s) - cycloaddition , chemistry , catalysis , azomethine ylide , selectivity , pyrrole , adduct , medicinal chemistry , ligand (biochemistry) , combinatorial chemistry , enantioselective synthesis , stereochemistry , 1,3 dipolar cycloaddition , organic chemistry , biochemistry , receptor
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐CC bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐ b ]pyrrole and the tetracyclic core of the alkaloid gracilamine.