Demchuk, Oleg M.Pietrusiewicz, Kazimierz MichałSzwaczko, KatarzynaMirosław, BarbaraDybała, IzabelaJasiński, Radomir2022-06-222022-06-222019"Molecules", 2019, Vol. 24, nr 3, 571http://hdl.handle.net/20.500.12153/3219A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the starting material. The palladium complexes of new ligands were obtained and characterised on the example of a crystalline dichloropalladium complex of [(1R,2R,9S,10S,11R,12R)-4-phenyltetracyclo[8.2.1.02,9.03,8]trideca-3,5,7-triene-11,12-diyl]bis(diphenylphosphane). A notably high activity and stereoselectivity of the palladium catalysts based on the new ligands were confirmed in a model asymmetric allylic substitution reaction. Herein, we discuss the geometry of the palladium complexes formed and its impact on the efficiency of the catalysts. A comparison of their geometric features with other bis(phosphane) ligand complexes found in the Cambridge Structural Database and built density functional theory (DFT) commutated models is also presented and rationalised.enUznanie autorstwa-Użycie niekomercyjne-Bez utworów zależnych 3.0 Polskahttp://creativecommons.org/licenses/by-nc-nd/3.0/pl/bis(phosphane) palladium complexmetallacycleNORPHOSallylic alkylationasymmetric catalysischiral phosphinesC-H bond activationpolycyclic compoundsstereoselective synthesisDFT calculationsinfo:eu-repo/semantics/article10.3390/molecules24030571