Chemistry of cyclic aminooxycarbenes

Abstract
A series of oxazolidin-2-ylidenes and one tetrahydro-1,3-oxazin-2-ylidene, generated by thermolysis of Δ3-1,3,4-oxadiazolines in benzene at 90 °C, were intercepted by insertion into the OH bond of phenols. In two cases the initial products rearranged to N-(2-aryloxyethyl)-N-methylformamides. The activation energy for rotation about the amide CN bond of those ultimate products was measured as 20.4 kcal/mol. The aminooxycarbenes reacted with two equivalents of methyl or phenyl isocyanate to give spiro-fused hydantoins. Major products from the reactions of the N-carbonyl carbenes with dimethyl acetylenedicarboxylate or with methyl propiolate were 2-oxazolines resulting from apparent acyl transfers from N to C in the proposed dipolar intermediates; minor products of 1:2 (carbene:trap) stoichiometry were also observed. Keywords: nucleophilic carbene, aminooxycarbene, oxadiazoline, amide rotation, oxazolidine.