Novel Water-Soluble Bisphosphinite Chiral Ligands Derived from α,α- and β,β-Trehalose. Application to Asymmetric Hydrogenation of Dehydroamino Acids and Their Esters in Water or an Aqueous/Organic Biphasic Medium

Yonehara, Koji; Hashizume, Tomohiro; Mori, Kenji; Ohe, Kouichi; Uemura, Sakae

doi:10.1021/jo990448m

Cited by 77 publications

(26 citation statements)

References 42 publications

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“…[8] This, despite the fact that sugar moieties could enhance water-solubility useful, for example, for the development of water-soluble catalysts and the biocompatibility of traditionally hydrophobic organometallic compounds. [9,10] On the other hand, organometallic metal cores often exhibit advantages in terms of kinetic inertness, stability, and size and thus could lead to the development of more efficient and stable compounds compared to ªclassicalº inorganic complexes.…”

Section: Introductionmentioning

confidence: 99%

Derivatization of Glucose and 2-Deoxyglucose for Transition Metal Complexation: Substitution Reactions with Organometallic99mTc and Re Precursors and Fundamental NMR Investigations

et al. 2001

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Synthetic strategies for the bifunctionalization of glucose and 2-deoxyglucose at position C-1 for transition metal coordination are reported. In particular organometallic technetium and rhenium complexes for potential use in diagnostic nuclear medicine were synthesized and investigated. Specifically, a common iminodiacetic acid (IDA) moiety was O-glycosidically connected through an ethylene spacer group to produce the pure alpha- (in case of 2-deoxyglucose) and beta-anomer (in case of glucose). Reaction of the sugar derivatives with the organometallic precursor [M(H2O)3(CO)3]+ (M = 99mTc, Re) produced single products in high yield, which are water-soluble and water-stable. The displacement of the three water molecules of the metal precursor and thus the tridentate coordination of the metal-tricarbonyl core exclusively via the amine and the two carboxylic acid functionalities of the IDA chelate was verified by means of 1D and 2D 1H NMR spectroscopy, mass spectrometry, and IR spectroscopy. The radioactive-labeled products (99mTc) proved their excellent stability in vitro in physiological phosphate buffer (pH = 7.4) and human plasma over a period of 24 h at 37 degrees C.

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Section: Introductionmentioning

confidence: 99%

Derivatization of Glucose and 2-Deoxyglucose for Transition Metal Complexation: Substitution Reactions with Organometallic99mTc and Re Precursors and Fundamental NMR Investigations

et al. 2001

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“…Rh-catalyzed asymmetric hydrogenation of aacetamidoacrylic and cinnamic acid derivatives afforded amino acids with up to 84% ee (S) (with ligand 119 a) and 72% ee (R) (with ligand 116 a), respectively [100]. The deprotected-hydroxyl diphosphinite ligand 119 e also enabled hydrogenation of enamides and itaconic acid in aqueous solution with enhanced enantioselectivities (ee-values up to 99%) [101]. Similar reports by RajanBabu showed its application with moderate to good enantioselectivity [102].…”

Section: Ar = Ph R = Hmentioning

confidence: 99%

Bidentate Ligands Containing a Heteroatom–Phosphorus Bond

Kok

Au‐Yeung

Cheung

et al. 2006

The Handbook of Homogeneous Hydrogenation

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Bidentate phosphorus ligands containing one or more heteroatom-phosphorus bonds are of high interest because they are relatively easy to prepare, and because a huge multitude of inexpensive, commercially available chiral diols, diamines, amino alcohols and amino acids can serve as the scaffold. Although the heteroatoms in these scaffolds are usually electronegative in nature, the reactivity and enantioselectivity of the metal complexes based on some of these ligands are quite remarkable, and sometimes even surpass those of the complexes based on electron-rich phosphines. This chapter compiles the comprehensive data concerning the asymmetric hydrogenation of various prochiral olefins mediated by the rhodium(I) complexes of this class of chiral ligands. Aminophosphine-Phosphinites (AMPPs)The ease of synthesis from chiral amino alcohols with a wide array of derivatives in one step established its good potential in the field of asymmetric catalysis. The general preparation of "semi-symmetrical" AMPPs involves the nucleophilic attack of two equivalents of chlorophosphine in the presence of a base (Fig. 27.1). A "mixed" AMPP can also be prepared by virtue of the fact that phosphorus-based electrophiles have a strong preference for hydroxy over secondary amine or amide. Clearly, this synthetic method allows the preparation of a large variety of AMPP ligands with adjustable electronic and steric properties. Agbossou recently reviewed the state of the art of AMPPs [1]. In consideration to the modern high-throughput methods, this approach allowed a rapid combinatorial screening of various catalysts and reactions.In general, applications of AMPP have concentrated on the asymmetric hydrogenation of functionalized olefins, especially dehydroamino acids. Among 883The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. Elsevier

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“…The d-manitol derived bisphosphinite ligand DIMOP, which was prepared by Chan, affords enantioselectivities of up to 97% ee for the hydrogenation of a-dehydroamino acids [73]. A water-soluble rhodium complex of the bisphosphinite ligand L11, which is derived from the b,b-trehalose backbone, provided an effective catalyst for the enantioselective hydrogenation of a-dehydroamino acid derivatives in water or an aqueous/organic biphasic medium (up to 99.9% ee) [74]. In order to rigidify the flexible structure of BI-NAPO, Zhang has recently reported a series of o-BINAPO ligands with substituents at the 3,3'-positions of the binaphthyl group [75].…”

Section: P-chiral Bisphosphane Ligandsmentioning

confidence: 99%

Rhodium‐Catalyzed Asymmetric Hydrogenation

Chi

Tang

Zhang

2005

Modern Rhodium‐Catalyzed Organic Reactions

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IntroductionMolecular chirality plays a very important role in science and technology. For example, the biological activity of many pharmaceuticals and agrochemicals is often associated with a single enantiomer. The increasing demand for enantiomerically pure pharmaceuticals, agrochemicals, and fine chemicals has therefore driven the development of asymmetric catalytic technologies [1, 2]. Asymmetric hydrogenation, using molecular hydrogen to reduce prochiral olefins, ketones, and imines, has become one of the most efficient, practical, and atom-economical methods for the construction of chiral compounds [3]. During the last few decades of the 20th century, significant attention was devoted to the discovery of new asymmetric catalysts, in which transition metals bound to chiral phosphorous ligands have emerged as preferential catalysts for asymmetric hydrogenation. Thousands of efficient chiral phosphorous ligands with diverse structures have been developed, and their application to asymmetric hydrogenation has been established. Indeed, many represent the key step in industrial processes for the preparation of enantiomerically pure compounds. The immense significance of asymmetric hydrogenation was recognized when the Nobel Prize in Chemistry was awarded to Knowles and Noyori.In this chapter, we focus on the rhodium-catalyzed hydrogenation and the development of chiral phosphorous ligands for this process. Although there are other chiral phosphorous ligands, which are effective for ruthenium-, iridium-, platinum-, titanium-, zirconium-, and palladium-catalyzed hydrogenation, they are not discussed in this account. However, this does not preclude complexes of other transition metals as effective catalysts for asymmetric hydrogenation. Fortunately, there are numerous reviews and books that discuss this particular aspect of asymmetric hydrogenation [3]. Chiral Phosphorous LigandsThe invention of efficient chiral phosphorous ligands has played a critical role in the development of asymmetric hydrogenation. To a certain extent, the development of asymmetric hydrogenation parallels that of chiral phosphorous ligands. The introduction of Wilkinson's homogeneous hydrogenation catalyst, [RhCl(PPh 3 ) 3 ][4], prompted the development of the analogous asymmetric hydrogenation by Knowles [5] and Horner [6] using chiral monodentate phosphine ligands, albeit with poor enantioselectivity. Kagan and Knowles each demonstrated that improved enantioselectivities could be obtained using bidentate chiral phosphine ligands. For example, Kagan and Knowles independently reported the C 2 -symmetric bisphosphine ligands, DIOP [7] and DIPAMP [8], for rhodium-catalyzed asymmetric hydrogenation. Due to its high catalytic efficiency in rhodium-catalyzed asymmetric hydrogenation of dehydroamino acids, DIPAMP was employed in the industrial production of l-DOPA [9]. Subsequently to this work, several other successful chiral phosphorous ligands were developed, as exemplified by Kumada's ferrocene ligand BPPFOH [10] and Achiwa's BPPM ligand [11]....

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Novel Water-Soluble Bisphosphinite Chiral Ligands Derived from α,α- and β,β-Trehalose. Application to Asymmetric Hydrogenation of Dehydroamino Acids and Their Esters in Water or an Aqueous/Organic Biphasic Medium

Cited by 77 publications

References 42 publications

Derivatization of Glucose and 2-Deoxyglucose for Transition Metal Complexation: Substitution Reactions with Organometallic99mTc and Re Precursors and Fundamental NMR Investigations

Derivatization of Glucose and 2-Deoxyglucose for Transition Metal Complexation: Substitution Reactions with Organometallic99mTc and Re Precursors and Fundamental NMR Investigations

Bidentate Ligands Containing a Heteroatom–Phosphorus Bond

Rhodium‐Catalyzed Asymmetric Hydrogenation

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