Directed (<i>R</i>)‐ or (<i>S</i>)‐Selective Dynamic Kinetic Enzymatic Hydrolysis of 1,2,3,4‐Tetrahydroisoquinoline‐1‐carboxylic Esters

Paál, Tihamér A.; Liljeblad, Arto; Kanerva, Liisa T.; Forró, Enikő; Fülöp, Ferenc

doi:10.1002/ejoc.200800789

Cited by 23 publications

(14 citation statements)

References 30 publications

(6 reference statements)

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“…As shown in Table , racemic substrates 2 a – 4 a were transformed into ( S )‐enantiomers at high conversions (up to >96%) and ee >99%. Compared with the alcalase‐catalyzed dynamic kinetic resolution of the racemic ester, the preparation of ( S )‐ 4 a using this cascade was more attractive in terms of the enantioselectivity and reaction efficiency.…”

Section: Resultsmentioning

confidence: 99%

Chemoenzymatic Approach to (S)‐1,2,3,4‐Tetrahydroisoquinoline Carboxylic Acids Employing D‐Amino Acid Oxidase

Qian

et al. 2019

Adv Synth Catal

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Optically pure 1,2,3,4‐tetrahydroisoquinoline carboxylic acids constitute an important class of building blocks for the synthesis of natural products and synthetic pharmaceuticals. However, redox deracemization of racemic 1,2,3,4‐tetrahydroisoquinoline carboxylic acids as an attractive method is still challenging for the lack of suitable oxidoreductases. Herein, a D‐amino acid oxidase from Fusarium solani M‐0718 (FsDAAO) with broad substrate scope and excellent enantioselectivity was exploited through genome mining, and applied for the kinetic resolution of a number of racemic 1‐ and 3‐carboxyl substituted tetrahydroisoquinolines to yield the corresponding (S)‐enantiomers with excellent enantiomeric excess (ee) values (up to >99%). By using FsDAAO in combination with ammonia‐borane in one pot, deracemization of these racemic carboxyl‐substituted tetrahydroisoquinolines was achieved with conversions up to >98% and >99% ee. Preparative‐scale deracemization of racemic 1,2,3,4‐tetrahydroisoquinoline‐1‐carboxylic acid and 1,2,3,4‐tetrahydroisoquinoline‐3‐carboxylic acid was also demonstrated with good isolated yields (82% and 73%, respectively) and ee>99%. Our study provides an effective method for the synthesis of enantiomeric pure 1,2,3,4‐tetrahydroisoquinoline carboxylic acids. This method is expected to provide access to chiral carboxyl‐substituted 1,2,3,4‐tetrahydroquinolines and 1,2,3,4‐tetrahydro‐ß‐carbolines.

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Section: Resultsmentioning

confidence: 99%

Chemoenzymatic Approach to (S)‐1,2,3,4‐Tetrahydroisoquinoline Carboxylic Acids Employing D‐Amino Acid Oxidase

Qian

et al. 2019

Adv Synth Catal

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“…[1,24,29,30] While azaemetines 5 and 14 behaved in a similar manner to their natural counterparts with respect to the chemical shift, line shape, and coupling pattern of the H-1' resonances, nuclear Overhauser effect (NOE) data indicated an unusual behavior for compounds 21 and 22. As in the natural series, one of the compounds (21) showed the downfield shifts in the A-ring observed for the iso-series, but failed to show the characteristic triplet for the H1' signal. However, its diastereomer 22 gave the doublet, which is characteristic for tubulosine (3), but did not show any anisotropic shielding by the A-ring.…”

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confidence: 81%

“…For the preparation of 14, the Fmoc-protected tetrahydroisoquinoline-1-carboxylic acid rac-16 obtained in five steps from homoveratrylamine was used as the coupling component for the northern half of the compound. [20][21][22] Acylation of amine 11 was achieved according to a modified Steglich protocol. [23] After removal of the Fmoc group, double reduction yielded 14 with high diastereoselectivity.…”

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confidence: 99%

Synthesis of Bioactive 2‐Aza‐Analogues of Ipecac and Alangium Alkaloids

et al. 2010

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“…The S absolute configuration is also in accordance, for instance, with the R enantiopreference previously observed in the CAL-B-catalyzed hydrolysis of 1,2,3,4-tetrahydroisoquinoline-1-carboxylic esters as determined by the Cahn-Ingold-Prelog priority rules. [11] Scheme 2. Preparation of (S)-8a for determining the enantiopreference of CAL-B.…”

Section: Determination Of Absolute Configurationsmentioning

confidence: 99%

Candida antarctica Lipase B in a Chemoenzymatic Route to Cyclic α‐Quaternary α‐Amino Acid Enantiomers

Li¹,

Rantapaju²,

Kanerva³

2011

Eur J Org Chem

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Kinetic resolution of three cyclic quaternary ethyl 1‐amino‐2,3‐dihydro‐1H‐indene‐1‐carboxylates and both 1‐ and 2‐amino‐1,2,3,4‐tetrahydronaphthalene analogues have been studied. Interesterification with butyl butanoate and Candida antarctica lipase B accomplished the task. The enantiomers of all 1‐amino analogues reacted with excellent enantioselectivity (enantiomeric ratio er greater than 200), whereas the 2‐amino analogue was not enantioselective (er = 4). Amino acid enantiomers were finally obtained as their respective hydrochlorides with almost maximum theoretical yields. For the first time, a lipase enzyme was effectively used in the kinetic resolution of cyclic α‐quaternary α‐amino esters.

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Directed (R)‐ or (S)‐Selective Dynamic Kinetic Enzymatic Hydrolysis of 1,2,3,4‐Tetrahydroisoquinoline‐1‐carboxylic Esters

Cited by 23 publications

References 30 publications

Chemoenzymatic Approach to (S)‐1,2,3,4‐Tetrahydroisoquinoline Carboxylic Acids Employing D‐Amino Acid Oxidase

Chemoenzymatic Approach to (S)‐1,2,3,4‐Tetrahydroisoquinoline Carboxylic Acids Employing D‐Amino Acid Oxidase

Synthesis of Bioactive 2‐Aza‐Analogues of Ipecac and Alangium Alkaloids

Candida antarctica Lipase B in a Chemoenzymatic Route to Cyclic α‐Quaternary α‐Amino Acid Enantiomers

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