Chiral Induction Effects in Ruthenium(II) Amino Alcohol Catalysed Asymmetric Transfer Hydrogenation of Ketones: An Experimental and Theoretical Approach

Petra, Daniëlle G. I.; Reek, Joost N. H.; Handgraaf, Jan‐Willem; Meijer, Evert Jan; Dierkes, Peter; Kamer, Paul C. J.; Brussee, Johannes; Leeuwen, Piet W. N. M. van

doi:10.1002/1521-3765(20000804)6:15<2818::aid-chem2818>3.3.co;2-h

Cited by 34 publications

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“…Early calculations in the 1970s on noncatalytic asymmetric induction demonstrated the usefulness of this type of calculations, even at a single‐point HF/STO‐3G level . One decade later, the first ab initio computation of a full reaction pathway of an organometallic catalyst system was reported, followed in the 1990s by the first DFT studies on asymmetric systems . Initially, these involved heavily truncated models, but the beginning of the new millennium saw calculations on full systems, also including solvent (PCM) effects.…”

Section: Discussionmentioning

confidence: 99%

“…With chiral elements incorporated into the amino‐alcohol ligand, ee's of up to 97% could be achieved (Scheme A) . Two essentially simultaneous QM studies of ruthenium‐catalyzed hydrogenations were reported: Andersson and coworkers (1999, ∼250 citations) and Petra et al (2000, ∼140 citations) . Subsequently, in 2001, Noyori and coworkers proposed selectivity‐determining interactions for this system on basis of QM calculations (∼230 citations by Jan. 2015, Web of Science) …”

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

“… Ruthenium‐amino‐alcohol‐catalyzed transfer hydrogenation of ketones. Experimental systems (1996, 1998, 2000) versus computational models used in mechanistic studies (1999, 2000).…”

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

“…Petra et al reported a combined experimental and theoretical study of Ru‐amino‐alcohol‐catalyzed transfer hydrogenation in 2000 . Calculations were performed with ADF (1999) and GAUSSIAN98 (Rev.…”

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

“…Petra et al first investigated the reaction mechanism and reported a cycle similar to the one shown in Scheme (at the time, Andersson's study was not yet published) . They then attempted to rationalize the selectivity, but noted that “ [a]symmetric catalysis is a challenge to theoretical investigations because it is sensitive to energy differences of less than 1 kcal mol − 1 .” This is particularly problematic when the estimated accuracy of the computed results is proposed to lie within a few kcal/mol . The preferred conformation of a chiral amino‐alcohol‐ruthenium complex was determined, followed by addition of acetophenone to the model.…”

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

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Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

Hopmann

2015

Int J of Quantum Chemistry

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Asymmetric catalysis is essential for the synthesis of chiral compounds such as pharmaceuticals, agrochemicals, fragrances, and flavors. For rational improvement of asymmetric reactions, detailed mechanistic insights are required. The usefulness of quantum mechanical studies for understanding the stereocontrol of asymmetric reactions was first demonstrated around 40 years ago, with impressive developments since then: from single-point Hartree-Fock/STO-3G calculations on small organic molecules (1970s), to the first full reaction pathway involving a metal-complex (1980s), to the beginning of the density functional theory-area, albeit typically involving truncated models (1990s), to current state-of-the-art calculations reporting free energies of complete organometallic systems, including solvent and dispersion corrections. The combined studies show that the stereocontrol in asymmetric reactions largely is exerted by nonbonding interactions, including CH/p attraction and repulsive forces. The ability to rationalize experimental results opens up for the possibility to predict enantioselectivities or to design novel catalysts on basis of in silico results.

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Section: Discussionmentioning

confidence: 99%

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

“… Ruthenium‐amino‐alcohol‐catalyzed transfer hydrogenation of ketones. Experimental systems (1996, 1998, 2000) versus computational models used in mechanistic studies (1999, 2000).…”

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

Section: Historical Perspective On Qm Studies Of Asymmetric Reactionsmentioning

confidence: 99%

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Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

Hopmann

2015

Int J of Quantum Chemistry

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Enantioselective Synthesis of α‐Trifluoromethyl Arylmethylamines by Ruthenium‐Catalyzed Transfer Hydrogenation Reaction

Dai

Cahard

2014

Adv Synth Catal

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A simple combination of dichloro(paracymene)ruthenium(II) dimer, a chiral amino alcohol and isopropyl alcohol allowed for in-situ generation of the bifunctional catalyst responsible for the transfer hydrogenation reaction of trifluoromethyl ket-A C H T U N G T R E N N U N G imines in excellent yields with high enantioselectivi-ties (up to 93% ee). Herein, we describe the optimization, scope, limitations, and applications of the method.

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Enantioselective Reduction of Aromatic and Aliphatic Ketones Catalyzed by Ruthenium Complexes Attached to β‐Cyclodextrin

Schlatter¹,

Kundu²,

Woggon³

2004

Angew Chem Int Ed

141

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Water‐soluble chiral Ru complexes with a β‐cyclodextrin unit have been shown to catalyze the reduction of aliphatic ketones (see scheme) with up to 97 % ee and in good to excellent yields in the presence of sodium formate. The β‐cyclodextrin unit is an essential component of the catalyst. It contributes to the unprecedented levels of enantioselectivity observed through the preorganization of the substrates in the hydrophobic cavity.

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Chiral Induction Effects in Ruthenium(II) Amino Alcohol Catalysed Asymmetric Transfer Hydrogenation of Ketones: An Experimental and Theoretical Approach

Cited by 34 publications

References 0 publications

Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples

Enantioselective Synthesis of α‐Trifluoromethyl Arylmethylamines by Ruthenium‐Catalyzed Transfer Hydrogenation Reaction

Enantioselective Reduction of Aromatic and Aliphatic Ketones Catalyzed by Ruthenium Complexes Attached to β‐Cyclodextrin

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