Industrial Synthesis of (+)-cis-Methyl Dihydrojasmonate by Enantioselective Catalytic Hydrogenation; Identification of the Precatalyst [Ru((−)-Me-DuPHOS)(H)(η6-1,3,5-cyclooctatriene)](BF4)

Dobbs, Daniel A.; Vanhessche, Koenraad P. M.; Brazi, Eric; Rautenstrauch, Valentin; Lenoir, Jean-Yves; Genêt, Jean‐Pierre; Wiles, Jason A.; Bergens, Steven H.

doi:10.1002/1521-3773(20000602)39:11<1992::aid-anie1992>3.0.co;2-w

Cited by 141 publications

(49 citation statements)

References 6 publications

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“…This 16-electron ruthenium center is usually stabilized by π-donation from the deprotonated ligand into the empty d-orbital. Hydrogen gas can then coordinate at this open site (III) producing a dihydrogen complex intermediate or transition state (11). The dihydrogen ligand heterolytically cleaves in step IV to re-form the original hydride complex 10.…”

Section: Proposed Mechanism For the Hydrogenation Of 35-bisarylidenementioning

confidence: 99%

“…[3][4][5] Many of them allow for the preferential reduction of carbon-carbon double bonds over a coexisting C=O functionality. [6][7][8][9][10][11] Catalysis is a multidisciplinary scientific concept that serves a broad range of industries covering specialty, fine, intermediate, commodity and life science chemicals. Catalysts are commonly used for the hydrogenation of alkenes, alkynes, aromatics, aldehydes, ketones, esters, carboxylic acids, nitro groups, nitriles and imines.…”

Section: Introductionmentioning

confidence: 99%

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Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Karaiskos¹,

Matiadis²,

Markopoulos³

et al. 2012

Hydrogenation

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Section: Proposed Mechanism For the Hydrogenation Of 35-bisarylidenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Karaiskos¹,

Matiadis²,

Markopoulos³

et al. 2012

Hydrogenation

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“…Firmenich established that (+)-cis-methyl dihydrojasmonate (Fig. 37.20) is the preferred stereoisomer, and subsequently developed an enantioselective process and began production on a multi-ton per year scale [82,83].…”

Section: Synthesis Of (+)-Methyl Cis-dihydrojasmonate (Firmenich)mentioning

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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“…The reaction of the Ru(g 3 -methylallyl) 2 (COD) complex with enantiopure diphosphines, and then with HBr, yields catalyst solutions thought to contain a solvated form of RuBr 2 (diphosphine) that are useful for the asymmetric hydrogenation of functionalized alkenes and ketones in- cluding unsaturated acids, b-ketoesters, and allylic alcohols [44,45]. The p-allyl complex can also be reacted with chiral diphosphines and HBF 4 /BF 3 to generate a very active hydrogenation catalyst for tetrasubstituted alkenes that are precursors to fragrances [46].…”

Section: Synthesis Of Ruthenium Precatalysts and Catalystsmentioning

confidence: 99%

Ruthenium and Osmium

Morris¹

2006

The Handbook of Homogeneous Hydrogenation

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Industrial Synthesis of (+)-cis-Methyl Dihydrojasmonate by Enantioselective Catalytic Hydrogenation; Identification of the Precatalyst [Ru((−)-Me-DuPHOS)(H)(η6-1,3,5-cyclooctatriene)](BF4)

Cited by 141 publications

References 6 publications

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Industrial Applications

Ruthenium and Osmium

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