ORIGINAL PAPER Aminoalkyl-phosphine (P,N) ligands with pentane-2,4-diyl backbone in asymmetric allylic substitution reactions Zso ´fia Csa ´sza ´r 1 • Patrik Imre 1 • Szabolcs Balogh 2 • Attila Be ´nyei 3 • Gergely Farkas 1 • Jo ´zsef Bakos 1 Received: 28 March 2017 / Accepted: 27 June 2017 / Published online: 20 October 2017 Ó Springer-Verlag GmbH Austria 2017 Abstract The asymmetric allylic substitution reaction of rac-1,3-diaryl-2-propenyl acetates with several C- and N-nucleophiles catalyzed by the palladium-complexes of eleven structurally analogous aminoalkyl-phosphines (P,N) with pentane-2,4-diyl backbone is reported. The role of the N-substituents and the influence of the ligand/palladium molar ratio on the activity and enantioselectivity of the catalytic system are studied. The solvent and the temper- ature dependence of the catalytic reaction were also assessed yielding enantioselectivities up to 95% in alky- lation and 90% in amination processes under optimized reaction conditions. Graphical abstract Keywords Homogeneous catalysis Á Alkylations Á Chiral auxiliaries Á Phosphorus compounds Á Transition metals compounds Introduction Asymmetric allylic substitution provides an efficient route for the enantioselective formation of C,C- and C-heteroa- tom bonds [1–6]. From another point of view, the palladium-catalyzed asymmetric substitution of allylic substrates is a typical benchmark reaction for the com- parison of new ligands. Consequently, there is a remarkable interest in this area, and a large number of new chiral ligands have been developed in the last few years [7–12]. Enantiomerically enriched alkylation and amina- tion products are formed from racemic substrates by different reactivities of the two allyl termini in the inter- mediate p-allyl systems. Desymmetrization of the allyl system can be performed by electronic and steric effects induced by the ligand(s) bound to the metal center [13]. For C 2 -symmetric systems, asymmetry arises only from steric interactions between the ligand and the substrate [14–17]. In the case of C 1 -symmetric ligands non-steric factors may become dominant as, for example, in those containing two distinct donor groups that differ in their coordination to the metal center. Consequently, asymmetric induction may chiefly occur as a result of the different trans influences of the donor atoms [18–23]. In transition metal complexes modified by heterobidentate aminoalkyl-phosphine (P,N) ligands the difference in the trans influence between the P and N donor atoms distinguishes the two binding sites mainly, making the substituent trans to the phosphorus more labile. Besides the extensively applied libraries of chiral P,N ligands like phosphino-oxazolines (a)[24–26], Electronic supplementary material The online version of this article (doi:10.1007/s00706-017-2029-2) contains supplementary material, which is available to authorized users. & Jo ´zsef Bakos bakos@almos.uni-pannon.hu 1 Department of Organic Chemistry, University of Pannonia, Egyetem u. 10, Veszpre ´m 8200, Hungary 2 NMR Laboratory, University of Pannonia, Egyetem u. 10, Veszpre ´m 8200, Hungary 3 Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem te ´r 1, Debrecen 4032, Hungary 123 Monatsh Chem (2017) 148:2069–2077 DOI 10.1007/s00706-017-2029-2