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The fate of branched and linear isomers in the rhodium-catalyzed hydroformylation of 3,4,4-trimethylpent-1-ene

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Abstract

In nonreversible hydroformylations, the computational evaluation of regio- and stereoselectivities from the relative energy barriers of the transition states (TS) for the alkyl-Rh intermediate formation step is possible, provided all low energy conformers are considered. In contrast, in reversible hydroformylations, also the subsequent reaction steps need to be taken into account to shed some light on mechanistic details. Thus, an extensive comparison of branched (B) and linear (L) reaction pathways for the Rh-catalyzed hydroformylation of 3,4,4-trimethylpent-1-ene (a bulky chiral substrate), going from a number of reactant complexes to products, has been carried out to rationalize the experimental result that pointed to reaction reversibility, although the value of the regioselectivity ratio (B:L = 15:85), based on alkyl-Rh TS free energies, computed under the hypothesis of nonreversibility, was in satisfactory agreement with the experimental one (5:95). A density functional theory approach at the B3P86/6-31G* level coupled to effective core potentials for Rh in the LanL2DZ valence basis set has been employed. By comparing the activation free energies involved in the various steps for the different reactant adducts, interestingly a similar behavior along all the linear pathways is found: the alkyl-Rh formation TS presents the highest barrier; thus, the reaction is nonreversible for all the linear isomers that invariably proceed to yield the linear aldehyde. Conversely, the behavior is quite different along the branched pathways. While some branched isomers eventually produce the corresponding aldehydes, two of the others follow distinct competing pathways, because β-hydride elimination occurs (a) to the terminal olefin-Rh complex (the starting material) that reacts again with the original regioselectivity, increasing the linear fraction, when the CO addition and insertion TS are higher than the alkyl-Rh TS and (b) to the internal olefin-Rh complex when the CO addition and insertion TS are higher than the relevant β-hydride elimination TS, but not than the alkyl-Rh TS. The solvent effect on the reversible profile, evaluated either in the supermolecule approach by adding a benzene molecule to the calculations or in the IEF-PCM framework (ε = 2.247), does not bring about any substantial change in the profile, leaving unaltered the conclusions reached.

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Notes

  1. Notice that to simplify the notation, only B3P86/6-31G* is reported throughout.

  2. Following the suggestion by Jonas and Thiel [46], who systematically investigated the performance of a variety of basis sets and methods (HF, DFT, and MP2) in transition metal carbonyls but Rh ones, we initially adopted BP86. Tests carried out in Ref. [28] on hydroformylations with Rh carbonyls supported the use of B3 instead.

  3. MP2 is often unreliable with transition metal systems [47, 48], if coupled to a basis set with limited virtual space, as is the case of 6-31G*.

  4. Occasionally, the CO groups in the plane roughly perpendicular to H–Rh–CO can swap their positions, thus inverting the pyramid orientation.

  5. Interestingly enough, the potential- and free-energy-based diastereoselectivity ratios (b:b′) are conversely very similar to each other, that is, 78:22 (ΔE) and 79:21 (ΔG); the difference between potential- and free-energy-based regioselectivity ratios thus depends on the linear regioisomers. Using a formula analogous to Eq. 2 and replacing b and b′ with the computationally available l and l′ populations, the two l:l′ potential- and free-energy-based diastereoselectivity ratios actually turn out to be 59:41 and 86.3:13.7, respectively.

  6. Thus two species react to give just one new compound.

  7. For branched structures, out of the two with a suitable orientation.

  8. The intermediate corresponding to “TSH2 b′2 in p” is “H2Int-b′2 in p” (reported in Table 6 and displayed in Fig. S8) that evolves to the branched aldehyde through “TS–H2 b’2 in p” (∆G=15.13 kcal/mol), that is, with a much higher barrier than when the hydrogens are in the basal CO plane.

  9. The most critical case because of TS relative values, involving β-elimination leading either to internal or initial olefin.

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  1. Molecular Modeling Lab, IPCF-CNR, Pisa UOS, Via Moruzzi 1, 56124, Pisa, Italy

    Giuliano Alagona & Caterina Ghio

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  1. Giuliano Alagona
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Correspondence to Giuliano Alagona.

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Dedicated to Professor Vincenzo Barone and published as part of the special collection of articles celebrating his 60th birthday.

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Alagona, G., Ghio, C. The fate of branched and linear isomers in the rhodium-catalyzed hydroformylation of 3,4,4-trimethylpent-1-ene. Theor Chem Acc 131, 1142 (2012). https://doi.org/10.1007/s00214-012-1142-x

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