Highly Efficient Asymmetric Hydrogenation of 2-Methylenesuccinamic Acid Using a Rh-DuPHOS Catalyst

Cobley, Christopher J.; Lennon, Ian C.; Praquin, and Céline; Zanotti‐Gerosa, Antonio; Appell, Robert B.; Goralski, and Christian T.; Sutterer, Angela

doi:10.1021/op0256183

Cited by 55 publications

(34 citation statements)

References 10 publications

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“…Upon testing, the crude product of the reaction between BINOL-based chlorophosphite and piperidine in the rhodium-catalysed hydrogenation of methyl 2-acetamido-cinnamate, we found that reaction was much slower and the product was obtained in only 60 % ee, whereas 99 % was obtained with pure 1 d. Evidently, the reason for this poor performance is the presence of a stoichiometric amount of chloride, which functions as a catalyst poison. [24] Remarkably, performing the coupling reaction in toluene and removing the salt by a simple filtration led to a crude ligand, which after removal of toluene performed quite satisfactorily in the above hydrogenation reaction. In this case, the conversion went to 100 % and the product was obtained with 96 % ee, which is only slightly lower as with the purified ligand.…”

Section: Instant Ligand Librariesmentioning

confidence: 99%

The Combinatorial Approach to Asymmetric Hydrogenation: Phosphoramidite Libraries, Ruthenacycles, and Artificial Enzymes

Vries¹,

Lefort²

2006

ChemInform

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Section: Instant Ligand Librariesmentioning

confidence: 99%

The Combinatorial Approach to Asymmetric Hydrogenation: Phosphoramidite Libraries, Ruthenacycles, and Artificial Enzymes

Vries¹,

Lefort²

2006

ChemInform

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“…Very few good results have been reported. Cobley and coworkers reported a hydrogenation process of 2 -methylenesuccinamic acid [189] . In addition to the high enantioselectivity achieved, the fast reaction rate and high turnover number of the process was signifi cant for industrial -scale synthesis.…”

Section: Unsaturated Acids and Their Derivativesmentioning

confidence: 99%

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Gao

Zhang

2010

Catalytic Asymmetric Synthesis

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INTRODUCTIONAmong all the catalytic asymmetric methodologies to chiral compounds, homogenous transition metal -catalyzed asymmetric hydrogenation plays a particularly important role [1] . Its highly effi cient, environmental friendly, and cost -effective natures have undoubtly made it one of the most studied methodologies during the past 40 years. As a result, the vast number of catalytic systems developed has also had a signifi cant impact on other areas of asymmetric catalysis [2] . More signifi cantly, the achievements from academia research on asymmetric hydrogenation were frequently acknowledged with industrial applications, which, in turn, provide an important driving force for its basic research [3] .Hundreds of catalytic systems have been developed since the seminal discoveries from Knowles and Sabacky [4] , Kagan and Dang [5] , and Horner et al. [6] . In many cases, series of chiral catalysts were developed based on the similar scaffolds and were prepared for the same reactions. Although these analogous ligands are more likely prepared for the purpose of patent protection other than academic curiosity, they indeed provide us an excellent opportunity to compare, evaluate, and study every aspect of the catalysts in asymmetric hydrogenation. In the meantime, a large number of prochiral unsaturated compounds have been successfully hydrogenated with excellent enantioselectivities. Practical applications with very low catalyst loadings and complex substrate structures have continued to emerge since the publication of the last edition of this book.

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“…RhDuPhos was used for itaconic amides by Dow/Chirotech [59,60] and gave eevalues of 96-97%, TON 100 000, TOF 13 000 h -1 at 45 8C, 10 bar. For dimethyl itaconates, Chiral Quest reported ee-values up to 99%, TON 5000, at r.t./1.5 bar using TangPhos [47], while Rh-catASium ® M (Degussa [61]) achieved ee-values up to 99%, TON 10 000, TOFs up to 40 000 h -1 at 25 8C/4 bar, and Rh-monophosphite (Lanxess [62]) gave ee-values up to 99%, TON 10 000, TOFs up to 5 000 h -1 at 0 8C/0.5 bar (ligand structures see Fig.…”

Section: Itaconic Acid Derivativesmentioning

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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Highly Efficient Asymmetric Hydrogenation of 2-Methylenesuccinamic Acid Using a Rh-DuPHOS Catalyst

Cited by 55 publications

References 10 publications

The Combinatorial Approach to Asymmetric Hydrogenation: Phosphoramidite Libraries, Ruthenacycles, and Artificial Enzymes

The Combinatorial Approach to Asymmetric Hydrogenation: Phosphoramidite Libraries, Ruthenacycles, and Artificial Enzymes

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Industrial Applications

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