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(a) For other successful chiral P,N‐ligands recently reported, see
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(a) Electronic effects in asymmetric catalysis with other types of ligands have been recently reported. Rh‐catalyzed hydrogenation:, Synlett
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(c) Ru‐catalyzed hydrogenation with BINAP‐type ligands:, 3064
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Substrate electronic effects were also observed (see also [4]). Thus, compared to styrene and in the presence of ligand 2a, para‐chlorostyrene and para‐methoxystyrene both gave lower ee's (93.5 and 79.2% ee, respectively). With ligand 2b the same two substrates afforded 13 and 77.6% ee, compared to 33.4% ee for styrene.
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Assuming a conservative NMR detection limit of 100:1 for two different compounds, such a difference in stability constant between the complexes containing 2g and 2b is inferred by comparing different pairs of ligands. These stability measurements, carried out on catalyst precursors, do not necessarily reflect the stabilities of the actual complexes involved in the catalytic cycle, but may be reasonably taken as an indication of the trend.
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However, the existence of a catalytically active complex containing the ferrocenyl ligand acting in a monodentate fashion under kinetic control cannot be excluded by these experiments.
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35
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(a) For general discussions of electronic effects in organic chemistry see, for example, 4th ed., Wiley, New York, Chapter 9, pp.
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