Nitrene-Transfer Reaction between Azide and Unsaturated Ether in the Presence of Pd(II) Catalyst

Abstract
Azidoformate reacted with allylic ethers to give 1-alkoxy-1-(alkoxycarbonylimino)alkane under catalysis by PdCl2(PhCN)2. The same imines were formed almost quantitatively by noncatalyzed reaction of the azide with the corresponding vinylic ethers. The rate of the catalyzed reaction was found to be first order each in the allylic ether and in the azide. Easiness of the imine formation from the allylic ethers depended on the nature of azide, decreasing in the order of N3SO2Me>N3CO2Me>N3Ph. Based on these results the most probable mechanism for the catalyzed reaction is proposed.

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