trans-[RuCl2(phosphane)2(1,2-diamine)] and Chiraltrans-[RuCl2(diphosphane)(1,2-diamine)]: Shelf-Stable Precatalysts for the Rapid, Productive, and Stereoselective Hydrogenation of Ketones

Doucet, Henri; Ohkuma, Takeshi; Murata, Kunihiko; Yokozawa, Tohru; Kozawa, Masami; Katayama, E.; England, Anthony F.; Ikariya, Takao; Noyori, Ryoji

doi:10.1002/(sici)1521-3773(19980703)37:12<1703::aid-anie1703>3.0.co;2-i

Cited by 602 publications

(291 citation statements)

References 4 publications

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“…18,67,68 However, simple unfunctionalized ketones are totally inert to this catalyst system, because the substrates are unable to stabilize the transition state by forming a chelate structure (Figure 1.15). 21 A combined system of trans-RuCl 2 (binap)(dpen) and alkaline base [84][85][86] or trans-RuH(Z 1 -BH 4 )-(binap)(dpen) 87 with or without a base exhibits excellent catalytic performance in asymmetric hydrogenation of a variety of simple ketones. 21,86 For example, acetophenone is hydrogenated in the presence of an (S)-XylBINAP/(S,S)-DPEN-Ru catalyst (ketone:Ru ¼ 100,000:1) in 2-propanol to give (R)-1-phenylethanol in 99% ee (Figure 1.17).…”

Section: Hydrogenation Of Simple Ketonesmentioning

confidence: 99%

Ligand Design for Catalytic Asymmetric Reduction

Ohkuma¹,

Kitamura²,

Noyori³

2006

New Frontiers in Asymmetric Catalysis

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Section: Hydrogenation Of Simple Ketonesmentioning

confidence: 99%

Ligand Design for Catalytic Asymmetric Reduction

Ohkuma¹,

Kitamura²,

Noyori³

2006

New Frontiers in Asymmetric Catalysis

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“…In addition, this reaction is rapid and productive. The hydrogenation of acetophenone with RuCl 2 [(R)-tolbinap][(R,R)-dpen] [(R,RR)-37] (DPENϭ1,2-diphenylethylenediamine) proceeds with a high turnover number of 2,400,000 and a high turnover frequency of 63 s Ϫ1 (47). This asymmetric hydrogenation has been ap- plied to the synthesis of various pharmaceutically important chiral compounds such as denopamine hydrochloride (25) (␤ 1 -receptor agonist), fluoxetine hydrochloride (26) (antidepressant), BMS 181100 (27) (antipsychotic), duloxetine (serotonin and norepinephrine inhibitor) (28), orphenadrine (29) (antihistaminic and anticholinergic), and neobenodine (30) (antihistaminic) (Fig.…”

Section: Metal-ligand Bifunctional Catalysismentioning

confidence: 99%

Toward efficient asymmetric hydrogenation: Architectural and functional engineering of chiral molecular catalysts

Noyori

Kitamura

Ohkuma

2004

Proc. Natl. Acad. Sci. U.S.A.

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266

105

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Asymmetric hydrogenation uses inexpensive, clean hydrogen gas and a very small amount of a chiral molecular catalyst, providing the most powerful way to produce a wide array of enantio-enriched compounds in a large quantity without forming any waste. The recent revolutionary advances in this field have entirely changed the synthetic approach to producing performance chemicals that require a high degree of structural precision. The means of developing efficient asymmetric hydrogenations is discussed from a mechanistic point of view.A symmetric catalysis lies outside the realm of traditional organic synthesis. It is a pervasive, global endeavor involving synthetic organic chemistry, catalytic chemistry, structural chemistry, inorganic and coordination chemistry, physical chemistry, and theoretical chemistry, as well as chemical engineering. Chiral Molecular Catalysts:Beyond the Shape Asymmetric catalysis is four-dimensional chemistry (1). High efficiency can be achieved only by using a combination of both an ideal 3D structure (x, y, z) and suitable kinetics (t). Currently, efficient asymmetric catalysis primarily uses a molecular catalyst that consists of a metallic element and chiral organic ligand(s) (2). Fig. 1 illustrates a typical (but not general) catalytic scheme. Under reaction conditions, the initially used precatalyst 1 is converted to the true catalyst 2 (induction process) that activates achiral molecules A and B and transforms them to the chiral product A-B (catalytic cycle). Although the ligand must create a distinct enantio-differentiating environment in transition metal-based complexes, such an architectural design does not suffice to achieve asymmetric catalysis. Some of the steps in the multistep transformation are reversible, whereas the first irreversible step, for example 334, kinetically determines the absolute stereochemistry of A-B. Efficient asymmetric catalysis requires a high turnover number and high turnover frequency, but the best way to generate high catalytic activity is not immediately apparent. First, the induction process of converting 1 to 2 is often not straightforward. Furthermore, to obtain a high turnover frequency, all of the transition metal-based entities 2-4 in this cycle must be neither very unstable nor very stable, avoiding substrate and͞or product inhibition. Instead, 2-4 are required to interconvert one another smoothly by means of a low kinetic barrier, and without any destructive side reactions. The reaction conditions strongly influence the stability and reactivity of 1-4. In general, both suitable architectural and functional engineering are crucial for obtaining sufficient catalytic efficiency. ''Molecular catalysis'' can cope with such requirements, because any molecules, by definition, can be designed and synthesized at will.This perspective deals largely with the intrinsic mechanistic aspects of asymmetric hydrogenation developed in our laboratories (3-5). Although HOH bonds are readily cleaved by transition metal complexes, truly useful asymmetric hydrogena...

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“…The RuCl1 distance trans to N1 is slightly shorter than the RuCl2 distance trans to P1 by 0.034 Å, and found to be 2.489 Å and 2.455 Å, respectively. In the crystal structure there are a number of RuCl···H2N contacts smaller than 3.0 Å, indicating the presence of unconventional intra-hydrogen bonds [7,13]. …”

Section: Discussionmentioning

confidence: 99%

“…The use of chiral Ru(II)(P-P)*(N-N)* complexes for asymmetric catalysis have been tremendously successful, especially in enantioselective hydrogenation of functionalized carbonyl compounds [2,[5][6][7][8], and there has been much interest in the chemistry of Ru(II) complexes bearing chiral diphosphine ligands such as BINAP [9]. Such complexes proved to be excellent catalysts in the hydrogenation of functionalized carbonyl compounds under mild condition [2][3][4][5][6][7][8][9][10][11]. The title complex [RuCl 2 (dppb)en] crystallizes with two CH 2 Cl 2 solvated molecules in full cis form with lost of the C 2 symmetry.…”

Section: Discussionmentioning

confidence: 99%

“…The title complex [RuCl 2 (dppb)en] crystallizes with two CH 2 Cl 2 solvated molecules in full cis form with lost of the C 2 symmetry. The cis-[RuCl 2(dppb)en] thermodynamical isomer is structurally favored over the trans-[RuCl 2(dppb)en] kinetic isomer [4,11,12], while the opposite was observed in solution and some solid state studies [3,[6][7][8]13]. The ruthenium center is in a distorted octahedral environment with a five-membered diamine ring coordinating in cis form via N1 and N2, a seven-membered bis(phosphine) ring coordinating in cis form via P1 and P2 as well as cis-dichloro coordination.…”

Section: Discussionmentioning

confidence: 99%

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Crystal structure of cis-dichloro-1,2-ethylenediamine-bis(1,4- (diphenylphosphino)butane)-ruthenium(II) dichloromethane disolvate, RuCl2(C2H8N2)(C28H28P2) · 2CH2Cl2

Warad¹

2007

Zeitschrift Für Kristallographie - New Crystal Structures

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C 32H40Cl6N2P2Ru, triclinic, P1 (no. 2), a = 10.338(6) Å, b = 13.024(5) Å, c = 14.491(5) Å, a = 81.02(2)°, b = 87.65(3)°, g = 66.95(3)°, V = 1772.9 Å 3 , Z = 2, R gt(F) = 0.028, wRref(F 2 ) = 0.075, T = 173 K. Source of materialAll the reactions were performed using Schlenk-type flask under argon and standard high vacuum-line techniques. [4,11,12], while the opposite was observed in solution and some solid state studies [3,[6][7][8]13]. The ruthenium center is in a distorted octahedral environment with a five-membered diamine ring coordinating in cis form via N1 and N2, a seven-membered bis(phosphine) ring coordinating in cis form via P1 and P2 as well as cis-dichloro coordination. The bis(phosphine) ring allows for PRuP angle to be larger than the ideal value of 94.13°, the smaller 1,2-diamine enforces NRuN angle that is 10.85°less than the ideal value, while the ClRuCl was found to be 89.61°which is very close to the ideal value. The RuN1 distance trans to Cl1 is shorter than the RuN2 distance trans to P2, 2.1213 Å and 2.1825 Å, respectively. The RuP1 distance trans to Cl2 slightly shorter than RuP2 distance trans to N2, 2.266 Å and 2.278 Å, respectively. The RuCl1 distance trans to N1 is slightly shorter than the RuCl2 distance trans to P1 by 0.034 Å, and found to be 2.489 Å and 2.455 Å, respectively. In the crystal structure there are a number of RuCl···H2N contacts smaller than 3.0 Å, indicating the presence of unconventional intra-hydrogen bonds [7,13].

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trans-[RuCl2(phosphane)2(1,2-diamine)] and Chiraltrans-[RuCl2(diphosphane)(1,2-diamine)]: Shelf-Stable Precatalysts for the Rapid, Productive, and Stereoselective Hydrogenation of Ketones

Cited by 602 publications

References 4 publications

Ligand Design for Catalytic Asymmetric Reduction

Ligand Design for Catalytic Asymmetric Reduction

Toward efficient asymmetric hydrogenation: Architectural and functional engineering of chiral molecular catalysts

Crystal structure of cis-dichloro-1,2-ethylenediamine-bis(1,4- (diphenylphosphino)butane)-ruthenium(II) dichloromethane disolvate, RuCl2(C2H8N2)(C28H28P2) · 2CH2Cl2

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