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Molecular Mechanics Predictions and Experimental Testing of Asymmetric Palladium-Catalyzed Allylation Reactions Using New Chiral Phenanthroline Ligands

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posted on 1996-05-08, 00:00 authored by Eduardo Peña-Cabrera, Per-Ola Norrby, Magnus Sjögren, Aldo Vitagliano, Vincenzo De Felice, Johan Oslob, Shingo Ishii, David O'Neill, Björn Åkermark, Paul Helquist
Molecular mechanics calculations were used to probe the conformational properties of a number of substituted phenanthrolines and their η3-allylpalladium complexes. Special attention was focused on phenanthrolines bearing chiral, terpene-derived, alkyl and alkenyl groups at C(2). Based upon these calculations, predictions could then be made regarding the suitability of the several ligands for use in asymmetric palladium-catalyzed substitution reactions of allylic acetates. Each of the substituted phenanthrolines was prepared by straightforward means. Use of these ligands in catalytic allylations gave results which were in good agreement with the calculation-based predictions. The highest levels of asymmetric induction were predicted and were obtained with a readily available 2-(2-bornyl)phenanthroline ligand 13. The results were compared with previously reported data obtained using other ligands. Overall, this work provides further indication of the potential utility of a combined calculational/experimental approach for the design of chiral catalysts.