- Allylic amination via decarboxylative C-N bond formation
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This manuscript details the development of a palladium-catalyzed allylic amination that proceeds via decarboxylation of allylic carbamates. Both saturated and aromatic heterocycles undergo decarboxylative rearrangement in good yields. The mechanism of allylation of heteroaromatic amines involves the formation of π-allyl palladium complexes followed by decarboxylation of the carbamate. Finally, the heteroaromatic anion equivalent is allylated to provide allylic amines. Georg Thieme Verlag Stuttgart.
- Mellegaard-Waetzig, Shelli R.,Rayabarapu, Dinesh Kumar,Tunge, Jon A.
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p. 2759 - 2762
(2007/10/03)
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- New Method for the Classification of Nucleophiles in the Palladium-Catalyzed Substitution of Allylic Acetates
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Palladium-catalyzed reactions of nucleophiles were carried out on cyclopent-2-enyl acetate (1), 3a,4,5,6,7,7a-hexahydro-(1α,3aα,4α,7α,7aα)-4,7-methano-1H-inden-1-yl acetate (3b), and 3a,4,5,6,7,7a-hexahydro-(1β,3aα,4α,7α,7aα)-4,7-methano-1H-inden-1-yl acetate (5b) to give indications on the mechanism of the reaction and the mode of attack of the nucleophiles.The lack of reactivity of 3b confirmed that a trans relationship between the approaching Pd(O) complex and the departing acetate is required in the η3-allyl-forming step.Examination of the reactivity of the nucleophiles with 5b compared to 1 allowed a decision as to whether the primary attack of the intermediate (η3-allyl)palladium complex by the nucleophile is directed to η3-allylic ligand (Nu1 nucleophiles: sodium dimethyl malonate, sodium cyclopentadienide, lithium thioxodiphenylphosphide, morpholide) or to the metal (Nu2 nucleophiles: phenylzinc chloride, sodium indenide, ammonium formate).
- Fiaud, Jean-Claude,Legros, Jean-Yves
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p. 1907 - 1911
(2007/10/02)
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- Nickel- and Palladium-Catalyzed Additions of Nucleophiles to Cyclic 1,3-Dienes
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Carbon nucleophiles have been found to add smoothly to 1,3-cyclohexadiene using either a preformed nickel-ligand complex or Ni(0) prepared by in situ reduction of Ni(II) in the presence of a ligand to give 1,2- and 1,4-addition products.Analogous adducts were also obtained from 1,3-cyclopentadiene and 1,3-cyclooctadiene, but the yields were considerably lower.Attempts to add benzenesufinic acid to 1,3-cyclohexadiene using Ni(0) were unsuccessful; this reaction was instead found to be catalyzed by Pd(0)-phosphite complexes.
- Andell, Ove S.,Baeckvall, Jan-E.,Moberg, Christina
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p. 184 - 189
(2007/10/02)
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- STEREOCHEMISTRY OF NUCLEOPHILIC ATTACK BY AMINE ON A CATIONIC Π-ALLYLNICKEL COMPLEX
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Reaction of the ?-allylnickel complex 3 with morpholine gave a 1:1 mixture of the amines 4 and 5 indicating that the amine has attacked the ?-allyl moiety from the side trans to nickel.
- Moberg, Christina
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p. 4539 - 4542
(2007/10/02)
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