1410788-11-2Relevant articles and documents
Insertion of allenes into the Pd-C bond of ortho-palladated primary arylamines of biological relevance: Phenethylamine, phentermine, (l)-Phenylalanine methyl ester, and (l)-tryptophan methyl ester. Synthesis of tetrahydro-3-benzazepines and their salts
Garcia-Lopez, Jose-Antonio,Saura-Llamas, Isabel,McGrady, John E.,Bautista, Delia,Vicente, Jose
, p. 8333 - 8347 (2013/02/22)
The previously reported ortho-metalated complexes [Pd(C,N-ArCH 2CRR'NH2-2)(μ-X)]2 derived from phenethylamine (Ar = C6H4, R = R' = H, X = Cl, Br), phentermine (Ar = C6H4, R = R' = Me, X = Cl), (l)-phenylalanine methyl ester (Ar = C6H4, R = H, R' = CO2Me, X = Cl, Br)), and (l)-tryptophan methyl ester (Ar = C 8H5N, R = H, R' = CO2Me, X = Cl) react with various allenes to give (1) the corresponding η3-allyl complexes derived from the insertion of one molecule of the allene into the Pd-C bond, the formation of which has been studied by DFT using a model complex, or (2) Pd(0) and the tetrahydro-3-benzazepinium salts, resulting from the decomposition of the above mentioned η3-allyl complexes, containing an exocyclic double bond, which, subsequently, react with a base to afford the corresponding benzazepines. The regiochemistry of these decomposition reactions has been studied and compared with that described for similar processes involving five-membered palladacycles. The crystal structures of the salts of some benzazepines and one isoquinoline, derived from a five-membered palladacycle, have been determined by X-ray diffraction studies.
