Temk&m Leaas, zyxwvutsrqponmlkjihgfedcbaZYXWVU Vol. 35, zyxwvutsrqponmlkjihgfedcbaZ No. zyxwvutsrqponmlkjihgfedcbaZY IO, pi. 1523-1526. 1994 Elscvier Sciabx Lad zyxwvuts hiINCdillGICSlBlitGl oo40-4039194 36.oo4.00 zyxwvuts tl@Kb4039(94~-H wy8is of Allyllc SubaWuUom by Pd Corn~lexom of Oxazolinas Contalnlng an Addttional P, S, or Se Center. X-Ray Cry&d StrucWw and Solution Structurw of Chlml re_Allyl PdWlum Comploxom of Phoophinoeryloxazollnes Jiirgen Sprinz, Matthias Kiefer and GOnter Heimchen’ Organ~mbch8m IndM der UnhferdMt, Im Newnh&w Feld 270, D-69120 Heideberg, FRQ Michael Reggelin OgaM&cbmbche8 In&M der UnhfentBt, Mariecwie-Str. 11,D-60439FwkhntAMn, FRQ Gottfried Huttner, Olaf Walter and Las& Zsoinai Ammkchn lnsthrt derUnlvusMt. Im Nwdwimer Fold270,D-691 20 Hekkberg,FAQ Abstract: Aiiylic alkylations with Pd complexes of chiral oxszolines with an additional donor P, S, or Se center are reported. Crystal and sofution structures of palladium tc-allyi complexes of phosphinoaryloxazolines were determined by X-ray crystaifography and cross relaxation a T timents, respectively. From the resulfs conclusions concerning the stertc course of allylic su stitutions are drawn. Recently we and others introduced phosphinoalkyi- and phosphinoaryloxazolines (1) as first mem- bers of a new class of chirai ligands. and demonstrated especially for the latter outstanding per- formance with respect to both reactlvlty and enanttoselectivlty in some Pd complex catalyzed alfylic substitution rsactionsl. in the meantime, we have prepared additional ligands by varying R and X of 1, widened the range of applications to La. N nucfeophiles and were able to determine crystal and solution structures for the x-ally1 Pd complexes 2, 3 and 4 that were previously describsdla. We hoped to aid by these studies mechanistic rationalization of the reactions of complexes 4 and analogous intermediates which required assessment of relative rates of reactions at Cl and C3 of the rapidly interconverting isomers 4x and 4n2. la-h X (ForRandX8faiablel) n 0 SbF, 1523