2004 Organo-phosphorus compounds

Organo-phosphorus compoundsS 0080 A Phosphorimidate Rearrangement for the Facile and Selective Preparation of Al-

lylic Amines. — Allylic phosphorimidates are prepared by reaction of an allylicalcohol, an azide, and a chlorophosphite. They undergo [3,3]-rearrangement under ther-mal conditions to provide single isomers of allylic phosphoramidates. This new process tolerates a range of substitution patterns on the reactants. Treatment of the products with ethanethiolate followed by acid hydrolysis results in formation of protected allylic amines [cf. (XI)]. Thus, the new strategy provides an attractive and versatile procedure for the preparation of allylic amines as key synthetic intermediates. — (CHEN, B.; MAPP*, A. K.; J. Am. Chem. Soc. 126 (2004) 17, 5364-5365; Dep. Chem., Univ. Mich., Ann Arbor, MI 48109, USA; Eng.) — S. Adam

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