Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 14, Issue 25, Pages 7699-7715Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200800559
Keywords
asymmetric catalysis; hydrogenation; ruthenium; water
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Funding
- DTI Manufacturing Molecules Initiatives (MMI)
- EPSRC [EP/C005643/1]
- MMI Project
- Engineering and Physical Sciences Research Council [EP/C005643/1] Funding Source: researchfish
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The mechanism of aqueousphase asymmetric transfer hydrogenation (ATH) of acetophenone (acp) with HCOONa catalyzed by Ru-TsDPEN has been investigated by stoichiometric reactions, NMR probing, kinetic and isotope effect measurements. DFT modeling and X-ray structure analysis. The chloride [RuCl-(TsDPEN)(p-cymene)] (1), hydride [RuH(TsDPEN)(p-cymene)] (3), and the 16-electorn species [Ru(TsDPENH)(p-cymene)] (4) were shown to be involved in the aqueous ATH, with 1 being the precatalyst, and 3 as the active catalyst detectable by NMR in both stoichiometric and catalytic reactions. The formato complex [Ru(OCOH)(TsDPEN)(p-cymene)] (2) was not observed; its existence, however, was demonstrated by its reversible decarboxylation to form 3. Both 1 and 3 were protonated under acidic conditions, leading to ring opening of the TsDPEN ligand. 4 reacted with water, affording a hydroxyl species. In a homogeneous DMF/H2O solvent, the ATH was found to be first order in the concentration of catalyst and acp, and inhibited by CO2. In conjunction with the NMR results, this suggests that hydrogen transfer to ketone is the rate-determining step. The addition of water stabilized the ruthenium catalyst and accelerated the ATH reaction; it does so by participating in the catalytic cycle. DFT calculations revealed that water hydrogen bonds to the ketone oxygen at the transition state of hydrogen transfer, lowering the energy barrier by about 4 kcal mol(-1). The calculations also suggested that the hydrogen transfer is more step-wise in nature rather than concerted. This is supported to some degree by the kinetic isotope effects, which were obscured by extensive H/D scrambling.
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