Asymmetric synthesis of (R)-(+)-6-(1,4-dimethoxy-3-methyl-2-naphthyl)-6-(4-hydroxyphenyl)hexanoic acid as a key intermediate for a neurodegenerative disease agent

Ikemoto, Tomomi; Nagata, Toshiaki; Yamano, Mitsuhisa; Itô, Tatsuya; Mizuno, Yukio; Tomimatsu, Kiminori

doi:10.1016/j.tetlet.2004.08.045

Cited by 26 publications

(16 citation statements)

References 16 publications

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“…

In terms of atom economy and environmental concerns, asymmetric hydrogenation of b,b-diarylacrylates with molecular H 2 is more advantageous.…”

mentioning

confidence: 99%

“…[3][4][5][6][7][8] Very recently, we disclosed that Rh I catalysts generated in situ by interaction with SPO preligands demonstrated excellent performance in the asymmetric hydrogenation of a-substituted ethenylphosphonic acids. [3][4][5][6][7][8] Very recently, we disclosed that Rh I catalysts generated in situ by interaction with SPO preligands demonstrated excellent performance in the asymmetric hydrogenation of a-substituted ethenylphosphonic acids.…”

mentioning

confidence: 99%

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Rhodium(I)‐Catalyzed Enantioselective Hydrogenation of Substituted Acrylic Acids with Sterically Similar β,β‐Diaryls

Li¹,

Dong²,

Wang³

et al. 2013

Angew Chem Int Ed

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Dedicated to Professor Guo-Qiang Lin on the occasion of his 70th birthdayOptically active b,b-diarylpropionic acids are a class of important building blocks for the asymmetric synthesis of chiral diarylmethine compounds, [1] which are structural moieties that are found in many pharmaceuticals and bioactive compounds, including the therapeutically important molecules tolterodine, [1a-b] sertraline, [1c] indatraline, [1d] and natural products, such as cherylline.[1e]Thus far, methods for the asymmetric synthesis of chiral b,b-diarylpropionic acids often involve a multistep sequence and/or stoichiometric transformation using chiral auxiliaries, [2] only a few examples of catalytic asymmetric methods, including Rh I -or Cu II -catalyzed reduction of b,b-diaryl unsaturated acrylates [3,4] or nitriles [5] using either polymethylhydrosiloxanes or diethoxymethylsilane as the reductants, and Rh I -catalyzed 1,4-addition of organoboron reagents to arylidene Meldrums acids, [6] have been reported to provide the corresponding b,b-diaryl propanoates or propanenitriles with good to high enantioselectivities. In terms of atom economy and environmental concerns, asymmetric hydrogenation of b,b-diarylacrylates with molecular H 2 is more advantageous. In this respect, Ir I -or Rh I -catalyzed asymmetric hydrogenation of trisubstituted olefins for the formation of diarylmethine stereogenic centers seems feasible. [7] However, reactions involving 3,3-diarylacrylates (especially free acids) proved to be challenging, as only moderate enantioselectivities were obtained, in most cases under high pressure (100 bar). Herein, we present the results of the development of an efficient asymmetric hydrogenation of b,b-diarylacrylic acids in the presence of a Rh complex based on the heterocombination of a chiral monodentate secondary phosphine oxide (SPO) preligand and an achiral monodentate phosphine ligand as the catalyst to afford a wide variety of the corresponding b,b-diarylpropionic acids with biological importance in excellent optical purities.The most challenging issue associated with the control of stereochemistry in the asymmetric hydrogenation of b,bdiarylacrylic acids is the differentiation of a stereogenic center with two sterically similar aryl groups at the b-position of acrylic acids. [3][4][5][6][7][8] Very recently, we disclosed that Rh I catalysts generated in situ by interaction with SPO preligands demonstrated excellent performance in the asymmetric hydrogenation of a-substituted ethenylphosphonic acids.[9] The salient features of SPO ligands, including ready accessibility, good air and moisture stability, and the potentially H-bonding OH group in the ligand, [9,10] prompted us to explore the catalytic potential of Rh I /SPO systems in the asymmetric hydrogenation of challenging b,b-diarylacrylic acid substrates. As shown in Table 1, chiral monodentate SPO preligands L1-L7 were evaluated in the rhodium-catalyzed asymmetric hydrogenation of (E)-3-phenyl-3-(p-tolyl) acrylic acid ((E)-1 a). However, an initial screening of ...

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“…

In terms of atom economy and environmental concerns, asymmetric hydrogenation of b,b-diarylacrylates with molecular H 2 is more advantageous.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

Rhodium(I)‐Catalyzed Enantioselective Hydrogenation of Substituted Acrylic Acids with Sterically Similar β,β‐Diaryls

Li¹,

Dong²,

Wang³

et al. 2013

Angew Chem Int Ed

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“…Feasibility studies were reported for the Rh-catalyzed asymmetric hydrogenation of a b,b-diarylsubstituted a,b-unsaturated acid, J001 giving the highest enantioselectivity (93% ee) [12] and for the hydrogenation of N-sulfonylated-a-dehydroamino acids using Ru/J002 (up to 99.1% ee), the first example of a Ru-catalyzed hydrogenation of a tetrasubstituted a-dehydroamino acid [13]. Mercks chemists also developed a mild and efficient route to chiral aryl alkyl amines via the Rh/Josiphoscatalyzed asymmetric hydrogenation of ene-trifluoroamides with 94-97% ee.…”

Section: Josiphosmentioning

confidence: 99%

Bidentate 1,2‐Ferrocenyl Diphosphine Ligands

Blaser¹,

Lotz²

2009

Chiral Ferrocenes in Asymmetric Catalysis

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IntroductionFerrocene as a (at the time rather exotic) backbone for chiral ligands was introduced by Kumada and Hayashi [1], based on Ugis pioneering work related to the synthesis of enantiopure ferrocenes (see Figure 4.1). PPFA as well as BPPFA and BPPFOH were not only the first ferrocene-based ligands but also the first ligands to exhibit both central and planar chirality and they proved to be very effective ligands for a variety of asymmetric transformations. From this starting point, several ligand families with a range of structural variations and types of chiral element have been developed in the last few years, very often starting from Ugi amine. In this chapter we will focus on the application of diphosphines developed over time where the two diphosphine moieties are attached to only one of the cyclopentadienyl (Cp) rings in a 1,2-arrangement. As a consequence these ligands can have a mix of chiral elements: planar chirality due to the ferrocene moiety, central chirality due to stereogenic carbon and/or phosphorus centers and, in one case, even axial chirality. Several recent reviews covering various aspects of ferrocene-based chiral ligands can serve to put the present account into a broader perspective [2]. Furthermore, we have recently summarized the synthetic procedures for most of the ligands described here [3].This chapter is organized according to the five types of arrangement of the two diphosphine moieties at the Cp ring (see Figure 4.2).Type A: Both PR 2 groups are directly attached to the Cp ring.Type B: One PR 2 group is directly attached to the Cp ring, the second PR 2 group is attached to the a position of a side chain.Type C: One PR 2 group is directly attached to the Cp ring, the second PR 2 group is attached to the b position of a side chain.

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“…Recently, DSM has divulged bench-scale results for the same transformation with a novel Rh-phosphoramidite-PPh 3 catalyst with somewhat lower enantioselectivity [76], and seemingly has applied the process on a production scale. While the catalytic performance of these two catalysts is adequate for manufacture, this is not (yet) the case for the examples of SmithKline Beecham [77] and Takeda Chemical Industries [78]; indeed, Takeda has developed an alternative technical process for the active ingredient.…”

Section: Allylic Alcohols and Ab-unsaturated Acidsmentioning

confidence: 99%

Industrial Applications

Blaser¹,

Spindler²,

Thommen³

2006

The Handbook of Homogeneous Hydrogenation

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While hydrogenation is without doubt the most important catalytic methodology for the manufacture of fine chemicals, until now most reactions have been carried out with heterogeneous catalysts. Heterogeneous hydrogenation catalysts have an exceptionally broad applicability for the chemo-and diastereoselective reduction of various functional groups, are convenient to handle, and catalyst separation is usually straightforward [1]. Homogeneous catalysts have found application for a number of special selectivity problems, the most important of which is enantioselective hydrogenation. While this will be the dominant topic of this chapter, a few scattered reports have been made where achiral complexes such as the Wilkinson catalyst, RhCl(Ph 3 P) 3 , or Ru-phosphine complexes have been applied on an industrial scale. In this regard, we will mention three examples [2]: (i) the chemoselective hydrogenation of a,b-unsaturated aldehydes; (ii) the diastereoselective hydrogenation of a tetracycline antibiotic; and (iii) the chemoselective hydrogenation of avermectin derivatives.As already mentioned, the most important industrial application of homogeneous hydrogenation catalysts is for the enantioselective synthesis of chiral compounds. Today, not only pharmaceuticals and vitamins [3], agrochemicals [4], flavors and fragrances [5] but also functional materials [6,7] are increasingly produced as enantiomerically pure compounds. The reason for this development is the often superior performance of the pure enantiomers and/or that regulations demand the evaluation of both enantiomers of a biologically active compound before its approval. This trend has made the economical enantioselective synthesis of chiral performance chemicals a very important topic.Industrial interest in the application of enantioselective catalysts began in earnest during the mid-1960s when the first reports of successful enantioselective transformations with homogeneous metal complexes were published. Within a surprisingly short period, production processes for two small-scale products, l-dopa (hydrogenation) and cilostatin (cyclopropanation) were developed and implemented by 1279The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. Elsevier

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Asymmetric synthesis of (R)-(+)-6-(1,4-dimethoxy-3-methyl-2-naphthyl)-6-(4-hydroxyphenyl)hexanoic acid as a key intermediate for a neurodegenerative disease agent

Cited by 26 publications

References 16 publications

Rhodium(I)‐Catalyzed Enantioselective Hydrogenation of Substituted Acrylic Acids with Sterically Similar β,β‐Diaryls

Rhodium(I)‐Catalyzed Enantioselective Hydrogenation of Substituted Acrylic Acids with Sterically Similar β,β‐Diaryls

Bidentate 1,2‐Ferrocenyl Diphosphine Ligands

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