Asymmetric synthesis of cis and trans 2-methyl and 2-ethyl 1-amino cyclopropanecarboxylic acids

Alami, A.; Calmès, Monique; Daunis, Jacques; Escale, Françoise; Jacquier, Robert; Roumestant, M. L.; Viallefont, Ph.

doi:10.1016/s0957-4166(00)82352-6

Cited by 39 publications

(8 citation statements)

References 23 publications

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“…-"~indered amine, i.e., iPr2EtN, and work-up with buffered water at pH 7 were used to avoid any racemization of the aldehyde. See ref.…”

Section: Methodsmentioning

confidence: 99%

“…Asymmetric syntheses of 1 -aminocyclopropanecarboxylic acid derivatives have recently been reported from the cycloaddition of diazomethane to a dehydro amino acid derivative using (lR,2R,SR)-2-hydroxy-3-pinanone as chiral auxiliary (7), from the cyclopropanation of optically active 3-alkylidene-1,4-oxazin-2-ones with (diethylamino)phenyloxosulfonium methylide (8), or from the stepwise dialkylation of the bislactim ethers of cyclo(~-Val-Gly-) and (L-tert-Leu-Gly-) with a large excess of trans-l,4-dichloro-2-butene (9) We have recently reported a new preparation of ACC based on the quantitative base-induced cyclization of a 2-imino-4-chlorobutyronitrile readily available from acrolein; this synthesis is suitable for large-scale preparations (1 1). We report herein an adaptation of this route to the general construction of the E 2-alkyl ACC frameworks that permits us to prepare these 2,3-methanoamino acids, in either d or 1 enantiomeric forms, in high optical purity, and which do not require any chiral auxiliary or cyclopropanating reagents.…”

Section: Omcrique a Partir De L'acttate De 2-(hydroxymcthyl)butyle (mentioning

confidence: 99%

“…(2). mide (DMF) was added dropwise, under argon, a solution of 5 g (42 mmol) of (2s)-methyl 3-hydroxy-2-methylpropionate 5 in 7.5 mL of (2R)-3-Chloro-2-methylpropan-1-01 7 DMF. The mixture was stirred for 12 h at room temperature and 120 To a solution of 400 mg (2.9 mmol) of (2R)-methyl 3-chloromL of ether and 12 mL of water were added.…”

Section: Synthesis Of (1s2s)-coronamic Acid 17mentioning

confidence: 99%

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Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Gaucher¹,

Ollivier²,

Marguerite³

et al. 1994

Can. J. Chem.

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(3R)-2-(N-Benzylideneamino)-4-chloro-3-methylbutyronitrile 3, prepared from the commercially available methyl (2S)-3-hydroxy-2-methyl propionate 5 (96% ee), readily underwent potassium carbonate induced cyclization to provide, after acid hydrolysis (6 N HCl) and chromatography, the (1S,2S)-norcoronamic acid 1a with 88% diastereoselectivity and > 95% enantiomeric excess. From (2R)-2-(hydroxymethyl)butyl acetate 23 (> 88% ee) obtained by enzymatic enantioselective hydrolysis with lipase PS, was prepared the (3S)-2-(N-benzylideneamino)-3-(chloromethyl)valeronitrile 29, which after base-induced cyclization (K2CO3) and acid (6 N HCl) or basic (0.8 N NaOH) hydrolysis led to the non-natural (1R,2R)-coronamic acid 18 (> 88% ee). Also from this same acetate (2R)-23 was prepared the (3R)-3-(chloromethyl)-2-[(diphenylmethylene)amino]pentanenitrile 37, which provided the (1S,2S)-coronamic acid 17 (> 88% ee) after base-induced cyclization (K2CO3 or LDA) and acid hydrolysis (6 N HCl). It is noteworthy that these short synthetic sequences, which do not require any expensive chiral auxiliary or optically active precursors, do not alter the enantiomeric purity of the stereogenic centers of these 2,3-methanoamino acids. However, the E diastereoselectivity of these cyclizations was not improved by using bulky N-(diphenylmethylene)amino substituent, contrary to results of some molecular mechanic calculations (MAD).

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“…-"~indered amine, i.e., iPr2EtN, and work-up with buffered water at pH 7 were used to avoid any racemization of the aldehyde. See ref.…”

Section: Methodsmentioning

confidence: 99%

Section: Omcrique a Partir De L'acttate De 2-(hydroxymcthyl)butyle (mentioning

confidence: 99%

Section: Synthesis Of (1s2s)-coronamic Acid 17mentioning

confidence: 99%

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Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Gaucher¹,

Ollivier²,

Marguerite³

et al. 1994

Can. J. Chem.

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“…NMR spectra showed that only the Z configuration was present. These dehydro compounds allowed the synthesis of cyclopropanic a-amino acids by cycloaddition with diazomethane (Alami et al, 1991) or by reaction with Corey's ylide (Calmes et al, 1996a). We describe here our results concerning Diels-Alder reactions on two dehydro compounds 6a (R = Me) and 6b (R = H) obtained by reaction of Eschenmoser's salt on oxazinone 3 in CH2CI: in 84% yield.…”

Section: Reactivity Of Chiral Schiff Basesmentioning

confidence: 97%

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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“…81 Condensation with aldehydes in tetrahydrofuran/potassium tert-butoxide at -78°C gives the (Z)-a,b-dehydroamino ester 47 (R = CH 3 , C 2 H 5 ) in 85% yield. 82 An aldol reaction or a reaction with an Eschenmoser salt gave rise to compounds 48. The cyclic glycine precursors came from the coupling of Boc-glycine with 2-hydroxyisovalerophenone (X = O) [83][84][85][86] or 2-aminoisovalerophenone (X = NBoc), [86][87][88] deprotection and cyclization with HCl and Me 3 N, and, in the case of X = NBoc, another Boc protection.…”

Section: Scheme 13 Synthesis Of Diketopiperazines 77mentioning

confidence: 99%

α,β-Dehydroamino Acids

Bonauer¹,

Walenzyk²,

König³

2006

Synthesis

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a,b-Dehydroamino Acids a , b -D e h y d r o a m i n o A c i d sAbstract: Dehydroamino acids are versatile intermediates in organic synthesis and occur as frequent structural motives in natural products and biologically active compounds. This review summarizes recent work (since 1999) on the synthesis, reactions and applications of acyclic and cyclic a,b-dehydroamino acids, a,bdehydroamino esters, and protected a,b-dehydroamino acids. 6Conclusions

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Asymmetric synthesis of cis and trans 2-methyl and 2-ethyl 1-amino cyclopropanecarboxylic acids

Cited by 39 publications

References 23 publications

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

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

α,β-Dehydroamino Acids

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