Synthetic applications of optically active cyanohydrins. Enantioselective syntheses of the hydroxyamides tembamide and aegeline, the cardiac drug denopamine, and some analogues of the bronchodilator salbutamol

Brown, R. F. C.; Donohue, Andrew C.; Jackson, W. R.; McCarthy, Tom D.

doi:10.1016/s0040-4020(01)85686-6

Cited by 54 publications

(20 citation statements)

References 41 publications

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“…The enzyme's reverse activity is used industrially in the enantioselective production of cyanohydrins. Cyanohydrins are valuable building blocks for the synthesis of fine chemicals, pharmaceuticals, and agrochemicals such as denopamine (β1-adrenergic receptor agonist) (3,4), clopidogrel (platelet aggregation inhibitor) (5), pyrethroids (insecticides) (6), and (R)-pantolactone [starting compound for synthesis of (R)-pantothenic acid, (R)-panthenol, and (R)-pantetheine] (7). The enantioselective condensation of benzaldehyde with hydrogen cyanide in the asymmetric synthesis of mandelonitrile using emulsin from the almond, Prunus amygdalus, as an HNL source (PaHNL), has been demonstrated (8).…”

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confidence: 99%

Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede,Chamberlinius hualienensis

Dadashipour

Ishida

Yamamoto

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

100

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Hydroxynitrile lyase (HNL) catalyzes the degradation of cyanohydrins and causes the release of hydrogen cyanide (cyanogenesis). HNL can enantioselectively produce cyanohydrins, which are valuable building blocks for the synthesis of fine chemicals and pharmaceuticals, and is used as an important biocatalyst in industrial biotechnology. Currently, HNLs are isolated from plants and bacteria. Because industrial biotechnology requires more efficient and stable enzymes for sustainable development, we must continuously explore other potential enzyme sources for the desired HNLs. Despite the abundance of cyanogenic millipedes in the world, there has been no precise study of the HNLs from these arthropods. Here we report the isolation of HNL from the cyanide-emitting invasive millipede Chamberlinius hualienensis, along with its molecular properties and application in biocatalysis. The purified enzyme displays a very high specific activity in the synthesis of mandelonitrile. It is a glycosylated homodimer protein and shows no apparent sequence identity or homology with proteins in the known databases. It shows biocatalytic activity for the condensation of various aromatic aldehydes with potassium cyanide to produce cyanohydrins and has high stability over a wide range of temperatures and pH values. It catalyzes the synthesis of (R)-mandelonitrile from benzaldehyde with a 99% enantiomeric excess, without using any organic solvents. Arthropod fauna comprise 80% of terrestrial animals. We propose that these animals can be valuable resources for exploring not only HNLs but also diverse, efficient, and stable biocatalysts in industrial biotechnology.millipede hydroxynitrile lyase | bioresource exploration | biocatalysis | white biotechnology | arthropod

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mentioning

confidence: 99%

Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede,Chamberlinius hualienensis

Dadashipour

Ishida

Yamamoto

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

100

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“…† Hydrogenation reactions, as well as analytical-scale (2 mL) and semi-preparative scale (5 mL) chemo-enzymatic one-pot transformations were carried out in magnetically stirred stainless steel autoclaves (16 mL total volume) that are part of a HEL PolyBlock8 parallel reactor system, and reactor temperature as well as stirring speed were controlled using the associated HEL WinISO software (v. 2.3.85.1). Gram-scale chemoenzymatic one-pot transformations were carried out in a Brown et al 1993Brown et al , 1994 3 3Asymmetric hydrocyanation (peptide catalyst) 72 14.6 483 30…”

Section: General Materials and Methodsmentioning

confidence: 99%

One-pot combination of enzyme and Pd nanoparticle catalysis for the synthesis of enantiomerically pure 1,2-amino alcohols

et al. 2013

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One-pot combinations of sequential catalytic reactions can offer practical and ecological advantages over classical multi-step synthesis schemes. In this context, the integration of enzymatic and chemo-catalytic transformations holds particular potential for efficient and selective reaction sequences that would not be possible using either method alone. Here, we report the one-pot combination of alcohol dehydrogenase-catalysed asymmetric reduction of 2-azido ketones and Pd nanoparticle-catalysed hydrogenation of the resulting azido alcohols, which gives access to both enantiomers of aromatic 1,2-amino alcohols in high yields and excellent optical purity (ee >99%). Furthermore, we demonstrate the incorporation of an upstream azidolysis and a downstream acylation step into the one-pot system, thus establishing a highly integrated synthesis of the antiviral natural product (S)-tembamide in 73% yield (ee >99%) over 4 steps. Avoiding the purification and isolation of intermediates in this synthetic sequence leads to an unprecedentedly low ecological footprint, as quantified by the E-factor and solvent demand.

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“…As a synthetic relevance of this asymmetric catalytic procedure, (R)-tembamide, a naturally occurring hydroxyamide (hypoglycemic agent) [16] isolated from various members of the Rutaceae family, [17] was synthesized from 4-methoxybenzaldehyde with nitromethane to give the corresponding nitroalcohol (A) in 88 % yield and 98 % ee on the 50 mmol scale (Scheme 4). Catalytic hydrogenation of A in the presence of 10 % Pd/C in methanol gave the corresponding amino alcohol (B) in 92% yield followed by condensation with benzoyl chloride; the final product was obtained in good yield and enantioselectivity.…”

Section: Variation Of Imine Concentrationmentioning

confidence: 99%

Enantioselective Henry and Aza‐Henry Reaction in the Synthesis of (R)‐Tembamide Using Efficient, Recyclable Polymeric Cu^II Complexes as Catalyst

et al. 2014

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Chiral copper(II) polymeric [H4]salen (salen=bis[(salicylidene)ethylenediaminato]) complexes CuII‐1–3 were generated in situ and used as efficient catalysts in the asymmetric Henry and aza‐Henry reaction of various aromatic and aliphatic aldehydes and N‐tosylimines in the presence of various nitroalkanes at room temperature (27±2 °C) for 20 hours. This group of polymeric [H4]salen complexes demonstrated excellent performance (product yield and enantiomeric excess ee up to 98 %) in the formation of β‐nitroalcohol by using nitromethane with low catalyst loading of 1 mol % (with respect to the monomeric salen unit) and high enantioinduction (ee 94 %) in the aza‐Henry product; β‐nitroamines were obtained with moderate yield (78 %). This catalytic system also worked well with nitroethane and 1‐nitropropane in the case of Henry reaction, to furnish the corresponding products in high yields and enantioselectivities for syn diastereomers. The CuII‐2 complex retained its performance at the gram level and was expediently recycled eight times with no significant loss in its performance. The kinetic study with CuII‐2 complex for the enantioselective aza‐Henry reaction of N‐Ts‐benzylimine (Ts=tosyl) revealed a first‐order dependence on catalyst and nitromethane concentration and was zero order with respect to the substrate. The product obtained was transformed straightforwardly to the pharmaceutically important enantiomerically pure (R)‐tembamide (β‐adrenergic agonist) drug in good yield by the asymmetric nitroaldol reaction of 4‐methoxybenzaldehyde in three successive steps.

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Synthetic applications of optically active cyanohydrins. Enantioselective syntheses of the hydroxyamides tembamide and aegeline, the cardiac drug denopamine, and some analogues of the bronchodilator salbutamol

Cited by 54 publications

References 41 publications

Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede,Chamberlinius hualienensis

Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede,Chamberlinius hualienensis

One-pot combination of enzyme and Pd nanoparticle catalysis for the synthesis of enantiomerically pure 1,2-amino alcohols

Enantioselective Henry and Aza‐Henry Reaction in the Synthesis of (R)‐Tembamide Using Efficient, Recyclable Polymeric Cu^II Complexes as Catalyst

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Synthetic applications of optically active cyanohydrins. Enantioselective syntheses of the hydroxyamides tembamide and aegeline, the cardiac drug denopamine, and some analogues of the bronchodilator salbutamol

Cited by 54 publications

References 41 publications

Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede,Chamberlinius hualienensis

Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede,Chamberlinius hualienensis

One-pot combination of enzyme and Pd nanoparticle catalysis for the synthesis of enantiomerically pure 1,2-amino alcohols

Enantioselective Henry and Aza‐Henry Reaction in the Synthesis of (R)‐Tembamide Using Efficient, Recyclable Polymeric CuII Complexes as Catalyst

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Enantioselective Henry and Aza‐Henry Reaction in the Synthesis of (R)‐Tembamide Using Efficient, Recyclable Polymeric Cu^II Complexes as Catalyst