A new enantiopure D-camphor-derived palladacycle

作者：Dickmu Gerard C; Stahl Lothar; Smoliakova Irina P^*

来源：Journal of Organometallic Chemistry, 2014, 756: 27-33.

DOI：10.1016/j.jorganchem.2014.01.011

• Palladacycle
• Enantiopure cyclopalladated complex
• D-Camphor O-methyloxime
• The (sp(3))C-Pd bond

D-Camphor O-methyloxime (HL, 1) was prepared as a 92: 8 mixture of E and Z isomers in 74% yield from D-camphor, methoxyamine hydrochloride and NaOAc in ethanol. Reaction of oxime 1 with Na2PdCl4 in a 2: 1 ratio in MeOH at rt provided the coordination complex PdCl2(HL)(2) (2) in 67% yield. Cyclopalladation of oxime 1 using Pd(OAc)(2) in acetic acid at 80 degrees C followed by treatment with LiCl furnished the chloro-bridged dimeric cyclopalladated complex [mu-ClPdL](2), 3, in 66% yield. Compound 3 was converted to the mononuclear PPh3 adduct 4 in 98% yield. The proposed structures of new complexes 2-4 were confirmed by H-1, C-13{H-1}, DEPT, and 2D NMR spectra. X-ray crystal study of complex 3 revealed the anti geometry of two cyclopalladated ligands as well as the presence of the (sp(3))C-Pd bond.

• 出版日期2014-4-15