title: Palladium-catalyzed allylic transposition of (allyloxy) iminodiazaphospholidines: a formal [3,3]-aza-phospha-oxa-Cope sigmatropic rearrangement for the stereoselective synthesis of allylic amines.
abstract: The synthesis of N-protected allylic amines has been achieved utilizing a palladium(II)-catalyzed, [3,3]-rearrangement of (allyloxy) iminodiazaphospholidines. This [3,3]-aza-phospha-oxa-Cope sigmatropic rearrangement reaction is thermodynamically driven by a P=N to P=O interconversion and is an alternative to the Overman rearrangement. The overall process involves the nucleophilic displacement of an allylic alcohol onto a P(III) precursor, followed by a Staudinger reaction to generate the (allyloxy) iminodiazaphospholidine precursors. Pd(II)-catalyzed [3,3]-aza-phospha-oxa-Cope rearrangement then gives a phosphoramide, which is readily hydrolyzed under acidic conditions to yield allylic amine derivatives. Pd(II) catalysis is believed to occur in a fashion analogous to that of the rearrangement of allylic imidates. The scope of racemic, diastereoselective, and enantioselective variants of this rearrangement is described. The use of chiral diamine auxiliaries in diastereoselective rearrangements is reported. Rearrangement of chiral N,N'-dimethyl cyclohexanediamine derived diazaphospholidines gives rise to phosphoramides with moderate diastereoselectivities (up to 3.5:1 dr). The same major diastereomeric product in these rearrangements was prepared irrespective of the starting allylic alcohol geometry. An enantioselective variant of the reaction was demonstrated for the rearrangement of cis-(allyloxy) iminodiazaphospholidines with cobalt oxazoline palladacycle (COP-X) catalysts (5 mol %) in high yield and enantioselectivity (up to 96% ee).
authors.affiliation: Department of Chemistry, University of Toronto, Toronto, Ontario, Canada.
authors.forename: Ernest E
authors.initials: EE
authors.lastname: Lee
authors.forename: Robert A
authors.initials: RA
authors.lastname: Batey
mesh_terms: D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D001372:Aza Compounds / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000138:chemical synthesis*; D010165:Palladium / Q000737:chemistry*; D010714:Phosphatidylethanolamines / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: C507248:(3,3)-aza-phospha-oxa-Cope; D000588:Amines; D001372:Aza Compounds; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D010714:Phosphatidylethanolamines; D010165:Palladium