Imidates rearrangement

Cohen F, Overman LE (1998) Planar-chiral cyclopalladated ferrocenyl amines and imines as enantioselective catalysts for allylic imidate rearrangements. Tetrahedron Asymmetry 9 3213-3222... 

Nomura H, Richards CJ (2007) An investigation into the allylic imidate rearrangement of trichloroacetimidates catalyzed by cobalt oxazoline palladacycles. Chem Eur J 13 10216-10224... 

Trifluoromethyl imidates show similar reactivity.262 Imidate rearrangements are catalyzed by palladium salts.263 The mechanism is presumably similar to that for the Cope rearrangement (see p. 555). 

Entry 6 is analogous to a silyl ketene acetal rearrangement. The reactant in this case is an imide. Entry 7 is an example of PdCl2-catalyzed imidate rearrangement. Entry 8 is an example of an azonia-Cope rearrangement, with the monocylic intermediate then undergoing an intramolecular Mannich condensation. (See Section 2.2.1 for a discussion of the Mannich reaction). Entry 9 shows a thioimidate rearrangement. 

Imidates, rearrangement of, 14, 1 Imines, additions of allyl, allenyl, propargyl stannanes, 64, 1 additions of cyanide, 70, 1 as dienophiles, 65, 2 synthesis, 70, 1 Iminium ions, 39, 2 65, 2 Imino Diels-Alder reactions, 65, 2 Indoles, by Nenitzescu reaction, 20, 3 by reaction with TosMIC, 57, 3 Ionic hydrogenation, 71, 1 Isocyanides, in the Passerini reaction, 65, 1... 

Preparation of J/V-Ac-Glu-VP[CF=CH]-Ala was also reported using the imidate rearrangement protocol [20]. 

W,A/-Diaikyi Ketene Aminai Rearrangements 8. OAllyl Imidate Rearrangement NR, nr, nr. 

V.A. Gilyarov, Amide-imide and imide-imide rearrangements-, Russ. Chem. Revs., 47, 870, 1978. 

Evidence has been obtained for palladacycles being catalyst precursors for soluble Pd(0) species and/or Pd nanoparticles.Palladacyles have been successfully employed as catalysts for alternating CO/alkene copo-lymerization. They have been amenable to allylic substitution,to oxygenation of unactivated sp C-H bonds,to allylic imidate rearrangement," " " " and to oxidation of alcohols to aldehydes and ketones." " ... 

Figure 5.6 Computed structures (B3LYP/LACVP +) and relative electronic energies with unsealed zero-point energy corrections (kcalmol" ) for the PdIMeCNjjClj-catalyzed allylic imidate rearrangement [14]. (Copyright 2007 American Chemical Society.)...

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