Reaction of Ynamides with Iminoiodinane-Derived Nitrenes: Formation of Oxazolones and Polyfunctionalized Oxazolidinones

This article describes the reaction
of ynamides with metallanitrenes
generated in the presence of an iodine­(III) oxidant. N-(Boc)-Ynamides are converted to oxazolones via
a cyclization reaction. The reaction is mediated by a catalytic dirhodium-bound
nitrene species that first behaves as a Lewis acid. The oxazolones
can be converted in a one pot manner to functionalized oxazolidinones
following a regio- and stereoselective oxyamination reaction with
the same nitrene reagent generated in stoichiometric amounts.

本文报道了炔酰胺（ynamides）与在三价碘氧化剂（iodine(III) oxidant）存在下生成的金属氮宾（metallanitrenes）之间的反应。N-叔丁氧羰基炔酰胺（N-(Boc)-Ynamides）可通过环化反应（cyclization reaction）转化为噁唑酮（oxazolones）。该反应由催化型双核铑结合氮宾物种（dirhodium-bound nitrene species）介导，该物种最初可作为路易斯酸（Lewis acid）发挥作用。所得噁唑酮可通过一锅法（one pot manner），与等化学计量比（stoichiometric amounts）生成的同种氮宾试剂发生区域及立体选择性氧胺化反应（regio- and stereoselective oxyamination），进而转化为官能化噁唑烷酮（functionalized oxazolidinones）。