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Copper‐Catalyzed Skeletal Rearrangement of O ‐Propargyl Oximes: A Mechanistic Manifold
Author(s) -
González Comesaña Marta,
Nieto Faza Olalla,
Cid María Magdalena,
Silva López Carlos
Publication year - 2016
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201600473
Subject(s) - substituent , chemistry , propargyl , oxime , reactivity (psychology) , olefin fiber , aryl , pyridine , moiety , medicinal chemistry , stereochemistry , catalysis , organic chemistry , medicine , alkyl , alternative medicine , pathology
The Cu‐mediated skeletal rearrangement of O ‐propargyl oximes features a mechanistic manifold that yields different compounds. Strategic modification of the substituent at the oxime moiety (R 3 ) allows the selection of a preferred mechanistic route that leads to azete oxides/amidodienes (if R 3 is an electron‐poor/‐rich aryl group) or to pyridine N ‐oxides (if R 3 is an olefin). In the present work, we explore the mechanism that leads to each product. All the computed mechanisms have in common an initial stepwise 2,3‐rearrangement that generates the key N ‐allenylnitrone intermediate the further reactivity of which will depend on the nature of the R 3 substituent. Our calculations reveal the subtle details that govern the different behavior of this reaction with each of the aforementioned substituents and disclose a complex and multistep pathway to different aminodienes.