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Computational prediction of selectivities in nonreversible and reversible hydroformylation reactions catalyzed by unmodified rhodium-carbonyls

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An Erratum to this article was published on 11 February 2012

Abstract

The regio- and stereoselectivities of the hydroformylation reaction catalyzed by an unmodified Rh catalyst have been investigated at the B3P86/6-31G* level with Rh described by effective core potentials in the LANL2DZ valence basis set for a number of either mono- or (1,1-, 1,2-, 1,3-) di-substituted substrates and compared with a variety of earlier results of ours, supplemented with free energy results when not already available. The computational prediction of regio- and stereoselectivities in nonreversible hydroformylations performed under mild reaction conditions is seemingly possible provided a careful conformational search for TS structures is carried out and all the low energy conformers are taken into account. The internal energy can be used to compute both the regio- and stereoselectivities in the hydroformylation of 1,1- and 1,3-substituted substrates with satisfactory results, whereas for 1,2-substituted substrates the regioselectivity determined from the internal energy is in good agreement with the experiment in the case of aliphatic olefins just for the lowest terms in the series (i.e., methyl and ethyl substituents), while the ratios are only qualitatively correct for the slightly bulkier iso-propyl and tert-butyl moieties. The theory/experiment agreement becomes decidedly better using the free energy differences instead.

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Scheme 1
Scheme 2
Scheme 3
Fig. 1
Fig. 2
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Notes

  1. Actually a chiral center appears in the hydroformylation of a nonchiral substrate when R (Scheme 1) is an alkyl group greater than CH3 or an aromatic group; the hydroformylation with unmodified rhodium catalysts however produces the racemic branched aldehydes without any stereoselectivity. In contrast, when the substrate is a chiral olefin itself, diastereoselectivity might originate as shown for two 1,3-substituted olefins in Scheme 2; notice that in such cases the total branched population is used to obtain the regioselectivity, because \( {\hbox{b}} + {\hbox{b}}\prime = {\hbox{B}}. \)

  2. The SBK(d) basis set is described in detail in Ref. 11.

  3. In those cases, 36 complex structures can be obtained, nine for each type (b, b’, l, l’). Taking into account the possible switch of the apical CO, as we did, the total number becomes 72.

  4. For the productories, both the B and L values are reported without an identical 10n factor.

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Authors and Affiliations

  1. Molecular Modeling Lab, CNR-IPCF (Institute for Physico-Chemical Processes), Via Moruzzi 1, 56124, Pisa, Italy

    Giuliano Alagona & Caterina Ghio

  2. DCCI (Department of Chemistry and Industrial Chemistry), University of Pisa, Via Risorgimento 35, 56126, Pisa, Italy

    Raffaello Lazzaroni

Authors
  1. Giuliano Alagona
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  2. Raffaello Lazzaroni
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  3. Caterina Ghio
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Correspondence to Giuliano Alagona or Caterina Ghio.

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An erratum to this article can be found at http://dx.doi.org/10.1007/s00894-012-1373-8.

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Alagona, G., Lazzaroni, R. & Ghio, C. Computational prediction of selectivities in nonreversible and reversible hydroformylation reactions catalyzed by unmodified rhodium-carbonyls. J Mol Model 17, 2275–2284 (2011). https://doi.org/10.1007/s00894-010-0864-8

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