Straightforward preparation of biologically active 1-aryl- and 1-heteroarylpropan-2-amines in enantioenriched form

Rodríguez‐Mata, María; Gotor‐Fernández, Vicente; González‐Sabín, Javier; Rebolledo, Francisca; Gotor, Vicente

doi:10.1039/c0ob00800a

Cited by 33 publications

(18 citation statements)

References 43 publications

(13 reference statements)

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“…[21] However, the reduction of the nitropropene derivatives, formed from the respective indole-carboxaldehydes, with lithium aluminium hydride proved to be successful. [4,18,[22][23][24] The yields were somewhat low, ranging from 5 to 21% but the synthetic methodology afforded sufficient quantities of the isomers for use as forensic standards. .…”

Section: Resultsmentioning

confidence: 99%

Identification of (2‐aminopropyl)indole positional isomers in forensic samples

Scott

Power

McDermott

et al. 2013

Drug Testing and Analysis

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In 2012, 5-(2-aminopropyl)indole (5-API, 5-IT) was reported by Norwegian authorities to the European Monitoring Centre for Drugs and Drug Addiction (EMCDDA) via the Early Warning System (EWS). The 3- isomer, 3-(2-aminopropyl)indole (3-API, AMT, alpha-methyltryptamine), has been available on the recreational drugs market for a somewhat longer time, having first been reported to the EMCDDA by Finnish authorities in 2001. Both isomers are available from online vendors of 'legal highs'. Recently, three forensic drug cases (two tablets and one powder) were presented for routine analysis and the active constituent was tentatively identified as an API isomer. The six positional isomers (2-, 3-, 4-, 5-, 6- and 7-(2-aminopropyl)indoles) were synthesized and analyses by a combination gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-mass spectrometry (LC-MS) showed that these could be readily discriminated thus facilitating the identification of 3-API in the tablets and 5-API in the powder. With exception of 5- and 6-APIs, which co-eluted, it was found possible to separate the isomers by GC without derivatization. LC separation also proved to be a feasible method for the discrimination of the isomers. Although the 2- and 7- isomers were not fully resolved by LC, it was found possible to distinguish them using their product ion spectra as the 2- isomer produced the m/z 132 fragment ion formed by loss of vinylamine, whereas the 7- isomer formed m/z 158 through loss of methylamine. In the synthesis 2-API, a novel tricyclic by-product was formed in an annulation reaction where the reaction solvent, tetrahydrofuran, was incorporated into the molecule.

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Section: Resultsmentioning

confidence: 99%

Identification of (2‐aminopropyl)indole positional isomers in forensic samples

Scott

Power

McDermott

et al. 2013

Drug Testing and Analysis

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“…However, acetone generated from isopropanol oxidation can condense with the substrate to give imines, whose subsequent reduction results in isopropylamines as byproducts. On the other hand, acyl donors such as alkyl methoxyacetates (Mavrynsky and Leino, 2014;Rodriguez-Mata et al, 2011;Veld et al, 2007) and benzyl carbonate (Hoben et al, 2008;Thalén et al, 2009) have been successfully applied in DKR reactions co-catalyzed by lipases and Ru. Alkyl methoxyacetates are more reactive than simple alkyl acetates towards lipase-catalyzed aminolysis, leading to faster reactions (Veld et al, 2007) while the use of carbonates produces carbamates, which can be easily hydrolyzed, thus allowing the recovery of the corresponding optically pure chiral amines under mild conditions after the DKR reaction (Hoben et al, 2008).…”

Section: Dynamic Kinetic Resolution Of Amines Catalyzed By Lipases Anmentioning

confidence: 99%

“…27) (Thalén et al, 2009); dynamic kinetic resolution of aromatic β-isopropylamines and bioactive heteroaromatic amines (Fig. 28) (Rodriguez-Mata et al, 2011).…”

Section: Dynamic Kinetic Resolution Of Amines Catalyzed By Lipases Anmentioning

confidence: 99%

Lipases: Valuable catalysts for dynamic kinetic resolutions

Miranda

Souza

2015

Biotechnology Advances

182

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“…[9] Thus, various families of biocatalysts have been efficiently employed in the asymmetric preparation of 1-arylpropan-2-amines using amine transaminases (ATAs), [10] amine dehydrogenases (AmDHs), [11] imine reductases (IREDs), [12] reductive aminases (RedAms) [13] or hydrolases such as lipases and proteases. [14] Particularly attractive are those methods developed through chemoenzymatic and multienzymatic ap-proaches, which allow to introduce higher molecular complexity. [15] For instance, Rebolledo and co-workers have reported the catalytic chemical oxidation of 1arylpropan-2-ols mediated by AZADO to produce the corresponding 1-arylpropan-2-ones, which were later subjected to asymmetric biotransamination using ATAs.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Synthesis of 1‐Arylpropan‐2‐amines from Allylbenzenes through a Wacker‐Tsuji Oxidation‐Biotransamination Sequential Process

2019

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Herein, a sequential and selective chemoenzymatic approach is described involving the metalcatalysed Wacker-Tsuji oxidation of allylbenzenes followed by the amine transaminase-catalysed biotransamination of the resulting 1-arylpropan-2-ones. Thus, a series of nine optically active 1-arylpropan-2-amines were obtained with good to very high conversions (74-92%) and excellent selectivities (> 99% enantiomeric excess) in aqueous medium. The Wacker-Tsuji reaction has been exhaustively optimised searching for compatible conditions with the biotransamination experiments, using palladium(II) complexes as catalysts and iron(III) salts as terminal oxidants in aqueous media. The compatibility of palladium/iron systems for the chemical oxidation with commercially available and made in house amine transaminases was analysed, finding ideal conditions for the development of a general and stereoselective cascade sequence. Depending on the selectivity displayed by selected amine transaminase, it was possible to produce both 1-arylpropan-2-amines enantiomers under mild reaction conditions, compounds that present therapeutic properties or can be employed as synthetic intermediates of chiral drugs from the amphetamine family.

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Straightforward preparation of biologically active 1-aryl- and 1-heteroarylpropan-2-amines in enantioenriched form

Cited by 33 publications

References 43 publications

Identification of (2‐aminopropyl)indole positional isomers in forensic samples

Identification of (2‐aminopropyl)indole positional isomers in forensic samples

Lipases: Valuable catalysts for dynamic kinetic resolutions

Stereoselective Synthesis of 1‐Arylpropan‐2‐amines from Allylbenzenes through a Wacker‐Tsuji Oxidation‐Biotransamination Sequential Process

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