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Nitrogen Nucleophiles in Au‐Catalyzed Dehydrative Cyclization Reactions
Author(s) -
Ketcham John M.,
Cardoso Flavio S. P.,
Biannic Berenger,
Piras Henri,
Aponick Aaron
Publication year - 2013
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201300041
Subject(s) - chemistry , nucleophile , allylic rearrangement , chirality (physics) , catalysis , cationic polymerization , carbamate , substrate (aquarium) , combinatorial chemistry , ring (chemistry) , alcohol , nitrogen , organic chemistry , symmetry breaking , chiral symmetry breaking , physics , oceanography , quantum mechanics , nambu–jona lasinio model , geology
Mild conditions for the gold‐catalyzed dehydrative cyclization of carbamate‐protected azaallylic alcohols to form saturated nitrogen heterocycles are reported. The cyclization reactions are high‐yielding, operationally easy to perform, and provide heterocycles with a synthetically useful vinyl group, strategically located on the ring system, which can facilitate further transformations for target oriented synthesis. It is also demonstrated through chirality transfer experiments that the mechanism can be either cationic in nature or a Au‐catalyzed addition/elimination sequence. The diverging mechanistic scenario is dependent on the nature of the substituents on the allylic alcohol and necessitates judicious substrate design.