Enantioselective Synthesis of 1,3-Dioxygen-substituted Chiral Building Blocks

Senanayake, Chris H.; Larsen, Robert D.; Bill, Timothy J.; Ji, Liu; Corley, Edward G.; Reider, Paul J.

doi:10.1055/s-1994-22793

Cited by 30 publications

(19 citation statements)

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“…This steric effect was revealed by comparison of the selectivity of the reaction conducted with catalysts bearing the SUNPHOS [30] family of ligands (Table 4, entries [5][6][7][8]. In all cases, full conversions were obtained and compound 1e was isolated in high yields ranging from 90-95%.…”

Section: Mol% Of [Ru(h)a C H T U N G T R E N N U N G (H 6 -Cot)synphos]mentioning

confidence: 97%

“…[2] 3-Hydroxy-2-methylpropionic acid methyl ester (1a) commonly named as Roche ester is a compound of significant synthetic interest. [3] Besides the currently used industrial enzymatic processes, [4] classical pathways to synthesize synthon 1a enantioselectively rely on oxidative degradation of a chiral homoallylic acetate, [5] diastereoselective addition of chiral alcohols to arylketenes, [6] or aldol chemistry. [7] However, there are some drawbacks associated with these methods such as the use of stoichiometric amounts of chiral auxiliaries, long reaction sequences and multiple tedious purification steps.…”

Section: Introductionmentioning

confidence: 99%

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Convenient General Asymmetric Synthesis of Roche Ester Derivatives through Catalytic Asymmetric Hydrogenation: Steric and Electronic Effects of Ligands

et al. 2008

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An efficient and concise asymmetric hydrogenation of acrylate esters promoted by the cat-+ BF 4 À is reported. A full investigation of the effects of catalyst precursors, solvents, temperature, hydrogen pressure, substrates as well as steric and electronic properties of ligands was carried out. The corresponding valuable Roche ester derivatives were obtained in good to excellent isolated yields and high enantioselectivities under mild conditions. The robustness and practicability of this highly enantioselective hydrogenation was demonstrated by the synthesis of the 3-hydroxy-2-methylpropanoic acid tert-butyl ester on a multigram scale, resulting in excellent yield and ee up to 94%.

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Section: Mol% Of [Ru(h)a C H T U N G T R E N N U N G (H 6 -Cot)synphos]mentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Convenient General Asymmetric Synthesis of Roche Ester Derivatives through Catalytic Asymmetric Hydrogenation: Steric and Electronic Effects of Ligands

et al. 2008

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“…Indeed, it has been previously reported that diastereoisomeric excesses of aryl propionic esters, resulting from the stereoselective addition of the alcohol to the corresponding ketene, are base- dependent (Salz and Riichard, 1982;Bellucci et al, 1988;Larsen et al, 1989;Senanayake et al, 1994;Calmes et al, 1994).…”

Section: Stereoselective Synthesis Of Amino Acid Derivatives Through mentioning

confidence: 99%

Some of the amino acid chemistry going on in the Laboratory of Amino Acids, Peptides and Proteins

et al. 1999

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Some of the chemistry of amino acids going on in our laboratory (Laboratoire des Amino acides Peptides et Protéines) is described as well as some mass spectrometry methodology for their characterization particularly on solid supports. Several aspects are presented including: (i) the stereoselective synthesis of natural and unnatural amino acids using 2-hydroxypinan-3-one as chiral auxiliary; (ii) the stereoselective synthesis of natural and unnatural amino acids by deracemization of alpha-amino acids via their ketene derivatives; (iii) the synthesis of alpha-aryl-alpha-amino acids via reaction of organometallics with a glycine cation; (iv) the diastereoselective synthesis of glycosyl-alpha-amino acids; (v) the synthesis of beta-amino acids using alpha-aminopyrrolidinopiperazinediones as chiral templates; (vi) the reactivity of urethane-N-protected N-carboxyanhydrides. To characterize natural and non natural amino acids through their immonium ions by mass spectrometry, some methodology is also described.

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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%). 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.…”

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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Enantioselective Synthesis of 1,3-Dioxygen-substituted Chiral Building Blocks

Cited by 30 publications

References 0 publications

Convenient General Asymmetric Synthesis of Roche Ester Derivatives through Catalytic Asymmetric Hydrogenation: Steric and Electronic Effects of Ligands

Convenient General Asymmetric Synthesis of Roche Ester Derivatives through Catalytic Asymmetric Hydrogenation: Steric and Electronic Effects of Ligands

Some of the amino acid chemistry going on in the Laboratory of Amino Acids, Peptides and Proteins

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

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