Asymmetric hydrogenation of unsaturated carboxylic acids catalyzed by BINAP-ruthenium(II) complexes

Ohta, Tetsuo; Takaya, Hidemasa; Kitamura, Masato; Nagai, Kazuya; Noyori, Ryoji

doi:10.1021/jo00390a043

Cited by 354 publications

(132 citation statements)

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“…1,2 Ru(OCOCH 3 ) 2 (binap) 18 catalyzes highly enantioselective hydrogenation of a variety of olefinic substrates such as enamides, a,b-and b,g-unsaturated carboxylic acids, and allylic and homoallylic alcohols (Figure 1.9). 6,7,[45][46][47][48] Chiral citronellol is produced in 300 ton quantity in year by this reaction. 9 It is worth noting that an opposite sense of enantioface selection is observed in going from the BINAP-Rh complex to the Ru catalyst.…”

Section: Hydrogenation Of Functionalized Olefins With Ruthenium Catalmentioning

confidence: 99%

Ligand Design for Catalytic Asymmetric Reduction

Ohkuma¹,

Kitamura²,

Noyori³

2006

New Frontiers in Asymmetric Catalysis

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Section: Hydrogenation Of Functionalized Olefins With Ruthenium Catalmentioning

confidence: 99%

Ligand Design for Catalytic Asymmetric Reduction

Ohkuma¹,

Kitamura²,

Noyori³

2006

New Frontiers in Asymmetric Catalysis

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“…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. 7) (48, 49).…”

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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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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“…With this aim in mind, we have recently focused our attention on the resolution of profens (Sonawane et al, 1992;Fuji et al, 1989;Larsen et al, 1989), such as ibuprofen (Alper & Hamel, 1990;Piccolo et al, 1991) and naproxen (Stille & Parrinello, 1993;Ohta et al, 1987;Kumar et al, 1991), using a novel parallel kinetic resolution methodology (Coumbarides, Dingjan, Eames, Flinn et al, 2006;Coumbarides, Dingjan et al, 2005;. For this project, we were required to determine the relative and absolute configurations of a series of related profen adducts derived from (+)-(4R,5S)-4-methyl-5-phenyl-2-oxazolidinone, (1).…”

Section: Commentmentioning

confidence: 99%