Neutral and Cationic Palladium Complexes of P-Stereogenic Phosphanes Bearing a Heterocyclic Substituent

作者：Clavero Pau; Grabulosa Arnald; Rocamora Merce; Muller Guillermo; Font Bardia Merce

来源：European Journal of Inorganic Chemistry, 2016, 2016(26): 4216-4225.

DOI：10.1002/ejic.201600608

The coordination chemistry of 13 optically pure P-stereogenic diarylmonophosphanes P(Het)PhR [Het = 4-dibenzofuranyl (DBF), 4-dibenzothiophenyl (DBT), 4-dibenzothiophenyl S,S-dioxide (DBTO2) and 1-thianthrenyl (TA); R = OMe, Me, iPr, Fc (ferrocenyl)] to Pd-allyl moieties is described. Both neutral [PdCl(eta(3)-(2-methylallyl)(kappa P-P)] and cationic [Pd{eta(3)-(2-methylallyl)(kappa P-P)(2)}]PF6 complexes have been prepared. Coordination of the heteroatom of the heterocycle was only possible in the case of TA-based phosphanes; these furnished complexes of the type [Pd{eta(3)-(2-methylallyl)(kappa P-2, S-P)}] PF6 after chloride abstraction with TlPF6. The crystal structure of the complex [Pd(eta(3)-2-methylallyl)(kappa P-2,S-PPh(OMe)(1-TA)]PF6 is reported. The neutral Pd complexes were found to be highly active in the hydrovinylation of styrene after activation with AgBF4, except for the TA-based phosphanes. The cationic Pd complexes were evaluated in allylic alkylation and amination with the model substrate ractrans-1,3-diphenylprop-2-enyl acetate (rac-I), achieving total conversions and up to 70 % ee.

• 出版日期2016-9