A unified approach to the tedanolides: Total synthesis of (+)-13-deoxytedanolide

Smith, Amos B.; Adams, Christopher M.; Barbosa, Stephanie A. Lodise; Degnan, Andrew P.

doi:10.1073/pnas.0402084101

Cited by 56 publications

(21 citation statements)

References 60 publications

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“…ing material by simply reversing the chirality of the desymmetrizing element. [10] Fukumoto and co-workers developed the first synthetic method to obtain desymmetrized 2-substituted-1,3-propanediols in high enantiomeric purity by employing chiral auxiliaries. [11,12] Oriyama and co-workers developed the first nonenzymatic catalytic desymmetrization using a proline-derived diamine to desymmetrize meso-2-alkyl-1,3-propane diols.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Zinc‐Catalyzed Asymmetric Desymmetrization of Acyclic 2‐Substituted‐1,3‐Propanediols: A Powerful Entry into Chiral Building Blocks

Trost

Malhotra

Mino

et al. 2008

Chemistry A European J

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The asymmetric acylation of meso 2-substituted-1,3-propanediols using an amphoteric chiral dinuclear zinc catalyst is described. It is has been demonstrated that both 2-alkyl-and 2-aryl-1,3-propanediols can be desymmetrized in high yields and enantioselectivities using the same family of ligands. Given that both antipodes of the chiral catalyst are available, both enantiomers of the desymmetrized product can be obtained from the same starting material.The synthetic utility of the desymmetrized products has been demonstrated by the synthesis of several chiral building blocks with high enantiomeric purities.

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Section: Introductionmentioning

confidence: 99%

Dinuclear Zinc‐Catalyzed Asymmetric Desymmetrization of Acyclic 2‐Substituted‐1,3‐Propanediols: A Powerful Entry into Chiral Building Blocks

Trost

Malhotra

Mino

et al. 2008

Chemistry A European J

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“…The latter is a popular chiral building block for the synthesis of vitamins (e.g., a-tocopherol [6] ), fragrance components (e.g., muscone [7] ), and antibiotics (e.g., calcimycin, [8] palinurin, [9] rapamycin, [10] 13-deoxytedanolide, [11] dictyostatin [12] ) and natural products (e.g., spiculoic acid A [13] ). Classical methods for its preparation include the diastereoselective addition of non-racemic alcohols as chiral auxiliaries, [14] the transformation of a chiral homoallylic acetate [15] or involve aldol condensation [16] and -most prominent -the transition metal-catalysed asymmetric hydrogenation of acrylate esters using Rh [17] (ee up to 99%) or Ru [18] (ee up to 94%).…”

mentioning

confidence: 99%

Asymmetric Synthesis of (R)‐3‐Hydroxy‐2‐methylpropanoate (‘Roche Ester’) and Derivatives via Biocatalytic CC‐Bond Reduction

et al. 2010

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Enoate reductases from the old yellow enzyme family were employed for the asymmetric bioreduction of methyl 2-hydroxymethylacrylate and its O-allyl, O-benzyl and O-TBDMS derivatives to furnish (R)-configurated methyl 3-hydroxy-2-methylpropionate products in up to > 99% ee Variation of the O-protective group had little influence on the stereoselectivity, but a major impact on the reaction rate.Keywords: biocatalysis; C=C-bioreduction; enoate reductase; old yellow enzyme; substrate engineeringThe asymmetric reduction of C=C bonds creates (up to) two chiral carbon centres and is thus one of the most widely employed strategies for the production of chiral materials. The biocatalytic variant, which is applicable to activated alkenes bearing an electron-withdrawing substituent is catalysed by enoate reductases [EC 1.3.1.X], [1,2] which are members of the old yellow enzyme (OYE) family.[3] Over the past few years, increasing attention has been devoted to these flavoproteins [4] in view of their substrate scope, [5] encompassing a,b-unsaturated carbonyl compounds (such as enals and enones), as well as carboxylic acids and derivatives thereof (such as esters, cyclic imides, nitriles, lactones) and nitroalkenes. As a rule of thumb, the degree of activation of the C=C-bond exerted by the electron-withdrawing effect of the activating substituent goes hand in hand with the substrate acceptance, which ensures generally fast reaction rates for enals, enones and nitroalkenes, whereas (di)carboxylic acids and esters are transformed more slowly.To illustrate the importance of this enzyme class for asymmetric synthesis, we aimed at their applicability for an industrially relevant product, that is, (R)-3-hydroxy-2-methylpropanoate, which is commonly denoted as the Roche ester. The latter is a popular chiral building block for the synthesis of vitamins (e.g., a-tocopherol [6] ), fragrance components (e.g., muscone [7] ), and antibiotics (e.g., calcimycin, [8] palinurin, [9] rapamycin, [10] 13-deoxytedanolide, [11] dictyostatin [12] ) and natural products (e.g., spiculoic acid A [13] ). Classical methods for its preparation include the diastereoselective addition of non-racemic alcohols as chiral auxiliaries, [14] the transformation of a chiral homoallylic acetate [15] or involve aldol condensation [16] and -most prominent -the transition metal-catalysed asymmetric hydrogenation of acrylate esters using Rh [17] (ee up to 99%) or Ru [18] (ee up to 94%). For the biocatalytic synthesis of the Roche ester only few examples are reported: the stereoselective oxidation of 2-methyl-1,3-propanediol by Gluconobacter and Acetobacter spp. [19] (ee up to 97%), the asymmetric reduction of ethyl 4,4-dimethoxy-3-methylcrotonate using bakers yeast [20] and the stereoseletive (formal) b-hydroxylation of isobutyric acid using Pseudomonas putida (ATCC 21244).[21] All of these biotransformations were performed using whole (fermenting) microbial cells with several enzymes being involved. Only recently, was it shown that a non-flavin NADH-dependen...

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“…A is a trisubstituted anionic substrate that is a precursor for chiral carboxylic acid derivatives reported as building blocks for the synthesis of an antitumoral prodrug and several adenosine antagonists . The hydrogenation product of B (known as the Roche ester) is a broadly applicable synthon used, for example, to make the antitumoral drugs tedanolide and discodermolide . Cyclic enamides C and D belong to the important class of aminotetralin precursors.…”

Section: Resultsmentioning

confidence: 99%

Combinatorial Strategies to find New Catalysts for Asymmetric Hydrogenation Based on the Versatile Coordination Chemistry of METAMORPhos Ligands

Terrade

Kluwer²,

Detz³

et al. 2015

ChemCatChem

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To extend the toolbox and find improved catalysts, anionic METAMORPhos ligands and neutral amino‐acid‐based ligands were used separately and in mixtures to form Rh complexes used in the asymmetric hydrogenation of eight industrially relevant substrates. Spectroscopic studies showed that under the catalytic conditions, the mononuclear complex with two different ligands (the heterocombination) is the main complex in solution if both the anionic and neutral ligands have the same chirality. If the neutral ligand and the anionic ligand have the opposite chirality at the P atom, monometallic and bimetallic heterocomplexes were detected by NMR spectroscopy and MS. For the majority of substrates evaluated in this study, higher enantioselectivities were obtained if the complexes used were based on the heterocombination of an anionic and a neutral ligand compared to respective homocombinations. After we found the initial leads, higher turnover numbers and enantioselectivities could be obtained easily by further exploring focused ligand libraries. The superior activity of the complexes based on the different ligands is highlighted by their robustness: significant divergence from a 1:1 ratio between the ligands does not lower the selectivity of the catalyst, although more of the competing homocomplexes are formed under these conditions.

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A unified approach to the tedanolides: Total synthesis of (+)-13-deoxytedanolide

Cited by 56 publications

References 60 publications

Dinuclear Zinc‐Catalyzed Asymmetric Desymmetrization of Acyclic 2‐Substituted‐1,3‐Propanediols: A Powerful Entry into Chiral Building Blocks

Dinuclear Zinc‐Catalyzed Asymmetric Desymmetrization of Acyclic 2‐Substituted‐1,3‐Propanediols: A Powerful Entry into Chiral Building Blocks

Asymmetric Synthesis of (R)‐3‐Hydroxy‐2‐methylpropanoate (‘Roche Ester’) and Derivatives via Biocatalytic CC‐Bond Reduction

Combinatorial Strategies to find New Catalysts for Asymmetric Hydrogenation Based on the Versatile Coordination Chemistry of METAMORPhos Ligands

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