O-Propargylic oximes

Scheme 114 Five-bond-cleavage rearrangement of O-propargyl oximes to P-lactams...

An unprecedent skeletal rearrangement of O-propargyl oximes has been reported to go via copper complex catalysis, involving cleavage of five different covalent bonds (C=N, N-O, C-O, C-C, and C=C) and leading to reorganization into (3-lactams in good to excellent yields (Scheme 114), [244]. 

Scheme 4.23 Oxazepine synthesis by copper-catalyzed intermolecular cascade reactions between O-propargylic oximes and dipolarophiles.

Nakamura, L, Kudo, Y, Terada, M. (2013). Oxazepine synthesis by copper-catalyzed intermolecular cascade reactions between O-propargylic oximes and dipolarophUes. Ange-wandte Chemie International Edition, 52, 7536-7539. 

O-Propargylic oximes that possess a proton at the a-position of the oxime group convert to the corresponding oxiranyl A-alkenylimines via a 5-endo-dig cyclization (Scheme 103). " (a ... 

Reaction with Propargyl Halides. The indium-mediated coupling of propargyl bromide with a variety of imines and imine oxides afforded homo-propargylamine derivatives in aqueous media under mild conditions.78 Propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(O) complex and indium(I) iodide in aqueous media was also studied (Eq.11.47).79... 

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