- Absolute configuration of anabasine from Messor and Aphaenogaster ants
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A method has been developed to assign the absolute configuration and enantiomeric excess of anabasine based on small amounts of material (in the microgram range), by derivatization with (+)-menthylchloroformate followed by capillary GC analysis of the resulting carbamate(s). This method was applied to three samples of anabasine isolated from Messor and Aphaenogaster ants. In Messor sanctus, only (2′S)-anabasine was present, whereas in Aphaenogaster subterranea and A. miamiana (2′S)-anabasine was determined to have an ee of 78 and 24%, respectively.
- Leclercq, Sabine,Charles, Sebastien,Daloze, Desire,Braekman, Jean-Claude,Aron, Serge,Pasteels, Jacques M.
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- Iridium-catalyzed asymmetric hydrogenation of 2-pyridyl cyclic imines: A highly enantioselective approach to nicotine derivatives
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A highly efficient asymmetric hydrogenation of cyclic imines containing a pyridyl moiety was established by using iridium catalysts with chiral spiro phosphine-oxazoline ligands. This process will facilitate the development of new nicotine-related pharmaceuticals. The introduction of a substituent at the ortho position of the pyridyl ring to reduce its coordinating ability ensures the success of the hydrogenation and excellent enantioselectivity.
- Guo, Cui,Sun, Dong-Wei,Yang, Shuang,Mao, Shen-Jie,Xu, Xiao-Hua,Zhu, Shou-Fei,Zhou, Qi-Lin
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Read Online
- Nicotine and pesticide poisonous chenopodium album method for the asymmetric synthesis of alkali
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The invention relates to an asymmetric synthesis method for botanical pesticide nicotine and anabasine. The low-cost and easily acquired 2,5-dibromopyridine is taken as an initial raw material and is processed in two steps, so that the hydrogenation precursor annular imine is acquired; under the induction of the chiral catalyst, iridium-phosphine oxazoline, an important hydrogenated product intermediate is acquired through high enantioselectivity; the intermediate is processed in two steps, so that L-nicotine is acquired; the intermediate is converted into L-anabasine in one step. The asymmetric hydrogenation of the annular imine containing pyridine gene is taken as the key step of the method. According to the invention, the chiral catalyst, iridium-phosphine oxazoline, is used for catalyzing the asymmetric hydrogenation and the key intermediate with ultrahigh ee value is acquired, and then the methylation and reduction bromine-removing two-step reaction is performed for converting, so that the target products, natural nicotine and anabasine, are acquired. According to the invention, the operation is stable, the purity is high and the cost is low.
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Paragraph 0017; 0029-0030
(2017/02/24)
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- Experimental and quantum-chemical studies of anabasine complexes with copper(II) and zinc(II) ions
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Anabasine copper(II) and zinc(II) complexes have been studied using experimental methods and quantum-chemical studies. Preferred coordination centers and possible structures of the complexes have been determined. It has been revealed, that the main coordi
- Bregier-Jarz?bowska, Romualda,Malczewska-Jaskó?a, Karolina,Jankowski, Wojciech,Jasiewicz, Beata,Hoffmann, Marcin,G?sowska, Anna,Jastrz?b, Renata
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p. 841 - 848
(2015/02/19)
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- Development of an R-selective amine oxidase with broad substrate specificity and high enantioselectivity
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Amine oxidases are useful bio-catalysts for the synthesis of enantiomerically pure 1°, 2° and 3° chiral amines. Enzymes in this class (e.g., MAO-N from Aspergillus niger) reported previously have been shown to be highly S selective. Herein we report the development of an enantiocomplementary R-selective amine oxidase based on 6-hydroxy-D-nicotine oxidase (6-HDNO) with broadened substrate scope and high enantioselectivity. The engineered 6-HDNO enzyme has been applied to the preparative deracemisation of a range of racemic amines to yield S-configured products, for example, (S)-nicotine, in high ee. Nicotine rush: An R-selective amine oxidase based on 6-hydroxy-D-nicotine oxidase (6-HDNO) with broadened substrate scope and high enantioselectivity has been developed. The engineered 6-HDNO enzyme is applied to the preparative deracemization of a range of racemic amines to yield S-configured products, for example, (S)-nicotine, in high ee.
- Heath, Rachel S.,Pontini, Marta,Bechi, Beatrice,Turner, Nicholas J.
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p. 996 - 1002
(2014/05/06)
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- Asymmetric synthesis of 2-heteroaryl cyclic amines: Total synthesis of (-)-anabasine
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A new and concise method for the synthesis of enantioenriched 2-heteroaryl cyclic amines was developed through an intramolecular chirality transfer. The influence of the nature of both ring size and heteroaryl moiety was investigated. The versatility of this reaction was demonstrated by the enantioselective synthesis of (-)-anabasine. Copyright
- Sallio, Romain,Lebrun, Stephane,Gigant, Nicolas,Gillaizeau, Isabelle,Deniau, Eric
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p. 4381 - 4388
(2014/07/21)
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- Application of catalytic dynamic resolution of N-Boc-2-lithiopiperidine to the asymmetric synthesis of 2-aryl and 2-vinyl piperidines
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The highly enantioselective synthesis of 2-aryl-and 2-vinyl-piperidines has been accomplished through a catalytic dynamic resolution (CDR) of N-Boc-2-lithiopiperidine. The method has been applied to the synthesis of both enantiomers of the tobacco alkaloid anabasine.
- Beng, Timothy K.,Gawley, Robert E.
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supporting information; experimental part
p. 394 - 397
(2011/04/12)
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- A stereoselective approach to 6-alkylated piperidinone & 2-piperidine via three-component vinylogous Mannich reactions (VMR) and a concise synthesis of (S)-anabasine
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A three-component diastereoselective vinylogous Mannich-type reaction (VMR) with the silyl ketene acetal (1) was developed. Adducts from the reactions provided valuable intermediates for construction of a variety of chiral 6-alkylated piperidinone and 2-piperidine compounds. The strategy was applied in a concise synthesis (S)-anabasine.
- Yang, Yang,Phillips, Dean P.,Pan, Shifeng
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scheme or table
p. 1549 - 1552
(2011/04/26)
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- Hydroformylation of homoallylic azides: A rapid approach toward alkaloids
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(Chemical Equation Presented) Unprecedented hydroformylation of homoallylic azides combined with useful one-pot operations provides an expeditive access to alkaloids.
- Spangenberg, Thomas,Breit, Bernhard,Mann, Andre
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supporting information; experimental part
p. 261 - 264
(2009/08/08)
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- A straightforward synthesis of (S)-Anabasine via the catalytic, enantioselective vinylogous mukaiyama-Mannich reaction
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The tobacco alkaloid (S)-anabasine was synthesized by a straightforward 4-step sequence with the catalytic enantioselective vinylogous Mannich reaction as a key step. Only 3 mol% of a structurally optimized chiral BINOL-based phosphoric acid was employed to control the absolute configuration of the natural product. Georg Thieme Verlag Stuttgart.
- Giera, David S.,Sickert, Marcel,Schneider, Christoph
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experimental part
p. 3797 - 3802
(2010/03/26)
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- Dynamic kinetic resolution and desymmetrization processes: A straightforward methodology for the enantioselective synthesis of piperidines
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A straightforward procedure for the synthesis of enantiopure polysubstituted piperidines is reported. It involves the direct generation of chiral non-racemic oxazolo[3,2-a]piperidone lactams that already incorporate carbon substituents on the heterocyclic ring and the subsequent removal of the chiral auxiliary. The key step is a cyclocondensation reaction of (R)-phenylglycinol or other amino alcohols with racemic or prochiral δ-oxo (di)acid derivatives in highly stereoselective processes involving dynamic kinetic resolution and/or desymmetrization of diastereotopic or enantiotopic ester groups.
- Amat, Mercedes,Bassas, Oriol,Llor, Nuria,Canto, Margalida,Perez, Maria,Molins, Elies,Bosch, Joan
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p. 7872 - 7881
(2007/10/03)
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- Stereoselectivity of the demethylation of nicotine piperidine homologues by Nicotiana plumbaginifolia cell suspension cultures
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The metabolism of (R,S)-N-methylanabasine and (R,S)-N-methylanatabine has been studied in a cell suspension culture of Nicotiana plumbaginifolia. Both substrates are effectively demethylated, anabasine or anatabine, respectively, accumulating in the medium. Similarly, there is strong stereoselectivity for the (R)-isomers of both substrates. The kinetics of metabolism of (R,S)-N-methylanabasine differ significantly from those of nicotine in that no further degradation of the initial demethylation product occurs. (R,S)-N-Methylanatabine, however, shows kinetics closer to those of nicotine, with loss of alkaloid from the system. Furthermore, (R,S)-N-methylanabasine does not diminish (S)-nicotine demethylation, indicating a lack of competition. However, the metabolism of (S)-nicotine is affected by the presence of (R,S)-N-methylanabasine. Hence, the demethylation of the piperidine homologues of nicotine is seen to be similar but not identical to that of the pyridine analogues. The implications of these different metabolic profiles in relation to the demethylation activity are discussed.
- Bartholomeusz, Trixie Ann,Molinie, Roland,Roscher, Albrecht,Felpin, Francois-Xavier,Gillet, Francoise,Lebreton, Jacques,Mesnard, Francois,Robins, Richard J.
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p. 1890 - 1897
(2007/10/03)
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- Enantioselective synthesis of 2-arylpiperidines from chiral lactams. A concise synthesis of (-)-anabasine
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Cyclodehydration of achiral or racemic aryl-δ-oxoacids with (R)-phenylglycinol stereoselectively affords chiral non-racemic bicyclic lactams, from which the enantiodivergent synthesis of (R)- and (S)-2-phenylpiperidine, the diastereodivergent synthesis of cis- and trans-3-ethyl-2-phenylpiperidine, and the enantioselective synthesis of the piperidine alkaloid (-)-anabasine is reported.
- Amat, Mercedes,Canto, Margalida,Llor, Nuria,Bosch, Joan
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p. 526 - 527
(2007/10/03)
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- 4-[(4'-Methylphenyl)sulfonyl]-1-(trophenylphosphoranylidene)-2-butanone as a New Four-Carbon Synthon for Substituted Divinyl Ketones
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The title compound and the corresponding anion have been conveniently used as precursors of substituted divinylketones in both carbo- and heterocyclization reactions in one-pot, three-step sequences leading to a wide variety of substituted carbo- and heterocyclic ring systems, as well as to multifunctionalized linear carbon frameworks. The compounds generated through the use of this multi-coupling reagent represent useful synthons for the construction of natural compounds including (+/-)-epibatidine, (-)-anabasine and (+/-)-pyrenophorin.
- Barco, Achille,Benetti, Simonetta,Risi, Carmela De,Marchetti, Paolo,Pollini, Gian Piero,Zanirato, Vinicio
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p. 975 - 986
(2007/10/03)
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- Efficient enantiomeric synthesis of pyrrolidine and piperidine alkaloids from tobacco
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An enantiomeric synthesis of six piperidine and pyrrolidine alkaloids, (S)-nornicotine 1, (S)-nicotine 2, (S)-anatabine 3, (S)-N-methylanatabine 4, (S)-anabasine 5, and (S)-N-methylanabasine 6, known as natural products in tobacco, was established from a common chiral homoallylic (S)-3-(1-azidobut-3-enyl)-pyridine 15. An intramolecular hydroboration-cycloalkylation of the homoallylic azide intermediate 15 served as the key step in the pyrrolidine ring formation. A ring closing metathesis reaction (RCM) of a diethylenic amine intermediate (S)-allyl-(1-pyridin-3-yl-but-3-enyl)-carbamic acid benzyl ester 20 served as the key step in the piperidine ring formation. From the commercially available 3-pyridinecarboxaldehyde 13, a short and convenient enantiomeric synthesis of tobacco alkaloids is described: (S)-nornicotine I (5 steps, with an overall yield of 70%), (S)-hicotine 2 (6 steps, 65%), (S)-anatabine 3 (8 steps, 30%), (S)-N-methylanatabine 4 (8 steps, 25%), (S)-anabasine 5 (8 steps, 35%), and (S)-N-methylanabasine 6 (8 steps, 25%).
- Felpin,Girard,Vo-Thanh,Robins,Villieras,Lebreton
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p. 6305 - 6312
(2007/10/03)
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- Total synthesis of (S)-anabasine and (S)-anatabine
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A chiral synthesis of (S)-anabasine and (S)-anatabine from 3-pyridinecarboxaldehyde, via a ring closing metathesis reaction (RCM) as the key step, is reported in 8 steps for both products with overall yields of 35% and 30%, respectively.
- Felpin,Vo-Thanh,Robins,Villieras,Lebreton
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p. 1646 - 1648
(2007/10/03)
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- A simple stereoselective synthesis of enantiopure 2-substituted pyrrolidines and piperidines from chiral (R)-phenylglycinol-derived bicyclic 1,3-oxazolidines
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Chiral, nonracemic 2-substituted pyrrolidines and piperidines were prepared in high ee and moderate to good chemical yields in three steps from (R)-phenylglycinol and γ- or δ-chloroketones. The key step of the synthesis was the stereo- selective reductive ring-opening of chiral bicyclic 1,3- oxazolidines prepared by condensation of (R)-phenylglycinol and the corresponding ketones.
- Andres, Jose M.,Herraiz-Sierra, Ignacio,Pedrosa, Rafael,Perez-Encabo, Alfonso
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p. 1719 - 1726
(2007/10/03)
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- Asymmetric aza-Diels-Alder reaction: Enantio- and diastereoselective reaction of imine mediated by Chiral Lewis acid
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An efficient asymmetric aza-Diels-Alder reaction using chiral boron mediator is developed. The key to its success is the use of the chiral boron complex prepared in situ from (R)- or (S)- binaphthol and B(OPh)3. The enantiomeric reaction of prochiral imine affords products of up to 90% ee. The double asymmetric induction of chiral imine using α-benzylamine as a chiral auxiliary is achieved with almost complete diastereoselectivity for both aliphatic and aromatic aldimines. This method is applied to the efficient synthesis anabasine and coniine of piperidine alkaloides.
- Hattori, Kouji,Yamamoto, Hisashi
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p. 1749 - 1760
(2007/10/02)
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- Asymmetric Aza-Diels-Alder Reaction Mediated by Chiral Boron Reagent
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An asymmetric aza-Diels-Alder reaction of an imine mediated by an in situ generated chiral boron complex is described.The method is successful with several aldimines and affords products of up to 90percent ee.
- Hattori, Kouji,Yamamoto, Hisashi
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p. 3264 - 3265
(2007/10/02)
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- Hetero-Diels-Alder Reactions on a Carbohydrate Template: Stereoselective Synthesis of (S)-Anabasin
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Diastereoselective aza-Diels-Alder reaction using the tetra-O-pivaloyl-β-D-galactopyranosylamine as the chiral template affords the synthesis of enantiomerically pure 2-substituted piperidine derivatives, e.g. the tobacco alkaloid (S)-anabasin.
- Pfrengle, Waldemar,Kunz, Horst
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p. 4261 - 4263
(2007/10/02)
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