Amine‐Tunable Ruthenium Catalysts for Asymmetric Reduction of Ketones

Rodrı́guez, Sonia; Qu, Bo; Fandrick, Keith R.; Buono, Frédéric G.; Haddad, Nizar; Xu, Yibo; Herbage, Melissa A.; Zeng, Xiaoming; Ma, Shengli; Grinberg, Nelu; Lee, Heewon; Han, Zhengxu S.; Yee, Nathan K.; Senanayake, Chris H.

doi:10.1002/adsc.201300727

Cited by 43 publications

(41 citation statements)

References 41 publications

(23 reference statements)

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“…[59][60][61] In Gaussian '09 calculations, this basis set has been shown to be an effective descriptor for ruthenium complexes. 62,63 . Solvation effects are included with the IEF-PCM model for water, 64 while anharmonic corrections were not included.…”

Section: Computational Methods and Detailsmentioning

confidence: 99%

Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

et al. 2016

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One of the key challenges in designing light-driven artificial photosynthesis devices is the optimisation of the catalytic water oxidation process. For this optimisation it is crucial to establish the catalytic mechanism and the intermediates of the catalytic cycle, yet a full description is often difficult to obtain using only experimental data. Here we consider a series of mononuclear ruthenium water oxidation catalysts of the formand its derivatives). The proposed catalytic cycle and intermediates are examined using density functional theory (DFT), radiation chemistry, spectroscopic techniques and electrochemistry to establish the water oxidation mechanism. The stability of the catalyst is investigated using Online Electrochemical Mass Spectrometry (OLEMS). The comparison between the calculated absorption spectra of the proposed intermediates with experimental ones, as well as free-energy calculations with electrochemical data, provides strong evidence for the proposed pathway: a water oxidation catalytic cycle involving four proton-coupled electron transfer (PCET) steps. The thermodynamic bottleneck is identified in the third PCET step involving the O-O bond formation. The good agreement between the optical and thermodynamic data with DFT predictions further confirms the general applicability of this methodology as a powerful tool in the characterisation of water oxidation catalysts and for the interpretation of experimental observables.2

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Section: Computational Methods and Detailsmentioning

confidence: 99%

Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

et al. 2016

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“…In 2004, Noyori and coworkers developed RuCl 2 (binap)(1,4‐diamine) complex‐catalyzed efficient asymmetric hydrogenation of 1‐tetralone derivatives with excellent results . In 2014, Rodríguez and coworkers explored chiral bisdihydrobenzooxaphosphole (BIBOP)/diamineruthenium complexes for the catalytic asymmetric hydrogenation of aryl and heteroaryl six‐membered cyclic ketones with good to excellent enantioselectivities . Therefore, it is necessary to develop a highly efficient catalytic system for the asymmetric hydrogenation of various benzo‐fused cyclic ketones with different ring sizes, affording enantioenriched benzo‐fused cyclic alcohols.…”

Section: Figurementioning

confidence: 99%

“…In addition, racemic α‐substituted benzo‐fused five to seven‐membered cyclic ketones were investigated, which involved dynamic kinetic resolution process ,,,. As shown in Scheme , racemic α‐methyl substituted benzo‐fused five/six‐membered cyclic ketones ( 3 a – 3 b ) worked well, providing the hydrogenation products ( 4 a – 4 b ) with high conversions, excellent enantioselectivities and good to excellent diastereoselectivities (98%–>99% conversions, 95%–96% yields, 99% ee, 81 : 19–95 : 5 dr).…”

Section: Figurementioning

confidence: 99%

Iridium/f‐Amphol‐catalyzed Efficient Asymmetric Hydrogenation of Benzo‐fused Cyclic Ketones

2018

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Iridium/f-Amphol-catalyzed asymmetric hydrogenation of various benzo-fused five to sevenmembered cyclic ketones was successfully developed, affording a series of chiral benzo-fused cyclic alcohols with excellent results (75%-99% yields, 93%-> 99% ee, and TON up to 297 000). The enantioenriched products can be employed as key intermediates or motifs for the synthesis of some important biologically active compounds, such as rasagiline mesylate TVP-1012 used for the treatment of Parkinson's disease, the enantiomer of anticonvulsant drug eslicarbazepine acetate (BIA 2-093).

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“…1,2 One efficient method for their synthesis is the catalytic hydrogenation of prochiral ketones and imines, respectively. [3][4][5][6][7][8][9] The source of the hydrogen for the iron catalyst described here (Figure 1) 10 is the solvent, isopropanol making this an asymmetric transfer hydrogenation (ATH) catalyst. The ketones and imines are reduced using this iron catalyst at 0.02 mol% catalyst loading for ketones and 1 mol% loading for imines as summarized in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and use of an asymmetric transfer hydrogenation catalyst based on iron(II) for the synthesis of enantioenriched alcohols and amines

Zuo

Morris

2015

Nat Protoc

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The catalytic hydrogenation of prochiral ketones and imines is an advantageous approach to the synthesis of enantioenriched alcohols and amines, respectively, which are two classes of compounds that are highly prized in pharmaceutical, fragrance and flavoring chemistry. This hydrogenation reaction is generally carried out using ruthenium-based catalysts. Our group has developed an alternative synthetic route that is based on the environmentally friendlier iron-based catalysis. This protocol describes the three-part synthesis of trans-[amine(imine)diphosphine]chlorocarbonyliron(II) tetrafluoroborate templated by iron salts and starting from commercially available chemicals, which provides the precatalyst for the efficient asymmetric transfer hydrogenation of ketones and imines. The use of the enantiopure (S,S) catalyst to reduce prochiral ketones to the (R)-alcohol in good to excellent yields and enantioenrichment is also detailed, as well as the reduction to the amine in very high yield and enantiopurity of imines substituted at the nitrogen with the N-(diphenylphosphinoyl) group (-P(O)Ph2). Although the best ruthenium catalysts provide alcohols in higher enantiomeric excess (ee) than the iron complex catalyst used in this protocol, they do so on much longer time scales or at higher catalyst loadings. This protocol can be completed in 2 weeks.

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Amine‐Tunable Ruthenium Catalysts for Asymmetric Reduction of Ketones

Cited by 43 publications

References 41 publications

Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

Iridium/f‐Amphol‐catalyzed Efficient Asymmetric Hydrogenation of Benzo‐fused Cyclic Ketones

Synthesis and use of an asymmetric transfer hydrogenation catalyst based on iron(II) for the synthesis of enantioenriched alcohols and amines

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