Journal of the American Chemical Society
Article
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under otherwise identical conditions, furnishes expected mixtures of γ-
and β-aldehydes with ratios of 74:26 and 76:24, respectively (at 56%
and >99% conversion, respectively). Again, the presence of separately
added anion receptor negligibly changes the outcome of these
reactions (providing a mixtures of γ- and β-aldehydes with ratios of
76:24 and 78:22, with 52% and >99% conversion, for 15 and 16,
respectively). Furthermore, hydroformylation of methyl ester ana-
logues of 15 and 16the substrates that do not bind to the
recognition center of L5catalyzed by the Rh/L5 catalyst also affords
mixtures of γ- and β-aldehydes with ratios of 62:38 and 73:27,
respectively, (at full substrate conversion). These experiments confirm
the importance of the noncovalent interactions in controlling the
selectivity of hydroformylation of allyl arene derivatives.
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(21) For an interesting alternative approach, developed by the groups
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covalent bonding of catalytic ligand-like directing groups, see:
̈
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(30) At the relatively high NMR concentration, and low pressure of
syngas (5 bar of CO/H2), the complex of ligand L3 is slowly
decomposing, however, as indicated by the HP IR studies, it seems to
be more stable at the catalytic conditions.
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(34) For details, see the SI.
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(36) Inhibition effect of various carboxylic acids on the hydro-
formylation of 1-hexene has already been reported, and the study
showed the more pronounced effect for more acidic benzoic acid
́ ́
derivatives, see: (a) Mieczynska, E.; Trzeciak, A. M.; Ziołkowski, J. J. J.
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(37) To characterize further the influence of the product on the
catalyst stability, we performed an additional experiment with the
prolonged catalyst incubation (20 h) in the presence of the product,
followed by substrate addition. In this case, the observed reaction rate
was about three times lower compared to experiments in which the
precatalyst was first activated in the absence of any acid, prior to the
addition of the mixture of the substrate and the product (SI Figure
S39). This shows that in the first experiment, two-thirds of the catalyst
got deactivated involving the presence of the product during the
incubation period of 20 h, and hence the catalyst half-lifetime under
these conditions is t1/2 ≈ 13 h. Similarly, precatalyst activation in the
presence of 4-heptylbenzoic acid results in the same level of catalyst
deactivation (SI Figure S39). As the catalyst is stable in the absence of
any carboxylate-containing compounds (>24 h), the deactivation
process likely involves also a carboxylate group of the product
molecule. Furthermore, a kinetic experiment under more challenging
conditions, that is at elevated temperature and with a very low catalyst
loading of 0.001 mol% Rh (substrate to catalyst ratio of 100 000:1)
shows that initially the reaction proceeds with a remarkable turnover
frequency of 18 000 mol mol−1 h−1 (5 turnovers per second!).
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(26) Although both the ligand and the aldehyde products are chiral,
there was no enantioselectivity observed in these reactions.
(27) Axet, M. R.; Castillon, S.; Claver, C. Inorg. Chim. Acta 2006,
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(28) For comparison, hydroformylation of substrates 15 and 16
catalyzed by a rhodium catalyst using PPh3 as a phosphorus ligand,
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dx.doi.org/10.1021/ja503033q | J. Am. Chem. Soc. 2014, 136, 8418−8429