Enantioselective Synthesis of Epoxy Amino Acids

Guillerm, D.; Lavrador, Karine; Guillerm, Georges

doi:10.1080/00397919508013424

Cited by 12 publications

(8 citation statements)

References 8 publications

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“…After being washed and chromatographed over silica gel (hexane–15% EtOAc), Boc-amino acid benzyl esters with side-chain epoxy group, benzyl (2 S )-2-Boc-amino-3-(2-oxiranyl)propionate isomers ((2 S )- 6 ) were obtained in 69% yield (Scheme 2). 34,35…”

Section: Resultsmentioning

confidence: 99%

“…These diastereomers were assigned with reference to the pure methyl (2 S ,4 S )-2-Boc-amino-3-(2-oxiranyl)propionate reported earlier. 35…”

Section: Resultsmentioning

confidence: 99%

“…Aer being washed and chromatographed over silica gel (hexane-15% EtOAc), Boc-amino acid benzyl esters with side-chain epoxy group, benzyl (2S)-2-Boc-amino-3-(2-oxiranyl)propionate isomers ((2S)-6) were obtained in 69% yield (Scheme 2). 34,35 Compound (2S)-6 was obtained as a diastereomeric mixture owing to the newly generated chiral center at C 4 , though these isomers were not separated under our TLC conditions. 1 H NMR spectra of (2S)-6 in CDCl 3 (Fig.…”

Section: Epoxidation Of Amino Acid Derivatives With Unsaturated Side ...mentioning

confidence: 92%

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Epoxy amino acids produced from allylglycines intramolecularly cyclised to yield four stereoisomers of 4-hydroxyproline derivatives

et al. 2014

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Derivatives of 2-amino-4-pentenoic acid (allylglycine) were efficiently resolved using Subtilisin or acylase.The side-chain unsaturated bond of the enantiomerically pure amino acid with tert-butoxycarbonyl (Boc) protection was smoothly epoxidized with m-chloroperbenzoic acid. When the Boc protection of the amino group was removed, the amino group intramolecularly attacked the side-chain epoxide, generating compounds with five-membered rings: the 4-hydroxyproline derivatives. Two diastereomeric products were formed through the cyclisation reaction, for example, (2S,4S)-4-hydroxyproline benzyl ester (cis-8) and (2S,4R)-4-hydroxyproline benzyl ester (trans-8) were formed from (2S)-amino acid with a side-chain epoxide. Compound (2S,4S)-4-hydroxyproline benzyl ester (cis-8) was transformed to a lactone (cis-hydroxyproline lactone, 10) with the removal of benzyl alcohol. The cis-conformation was essential for the intramolecular ester exchange reaction; in fact, no lactone formation was observed for the trans isomer (trans-8). The separation of cis-hydroxyproline lactone and the trans-isomeric hydroxyproline benzyl ester was facile and clear, in contrast to the difficult separation of cis-and transhydroxyproline derivatives. Thus, two diastereomers of hydroxyproline derivatives for L-hydroxyproline and also for D-hydroxyproline were obtained, i.e., four diastereomers of hydroxyproline derivatives.

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Section: Resultsmentioning

confidence: 99%

“…These diastereomers were assigned with reference to the pure methyl (2 S ,4 S )-2-Boc-amino-3-(2-oxiranyl)propionate reported earlier. 35…”

Section: Resultsmentioning

confidence: 99%

Section: Epoxidation Of Amino Acid Derivatives With Unsaturated Side ...mentioning

confidence: 92%

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Epoxy amino acids produced from allylglycines intramolecularly cyclised to yield four stereoisomers of 4-hydroxyproline derivatives

et al. 2014

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“…Attempts to purify the compound for characterization studies were unsuccessful, possibly due to competing dlactam formation. Hence, the crude product of reductive hydrogenation of azidolactone 4 was directly treated with 20 and triethylamine in the presence of 2-chloro-N-methylpyridinium iodide, 21 giving 6 with a yield of 70%. Although it was easier to isolate product 6 when the guanylation of amine 5 was carried out in the presence of mercuric chloride rather than 2-chloro-N-methylpyridinium iodide, the yield was quite variable.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of [guanido‐¹³C]‐γ‐hydroxyarginine

Yoon

Zabriskie

Cheon

2008

Labelled Comp Radiopharmac

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This report describes an efficient method of synthesizing [guanido-13 C]-c-hydroxyarginine HCl salt. Iodolactonization of N-Boc-protected allylglycine mainly provided the cis iodo compound 2. This was converted to an amine through azide 4. The amine 5 was reacted with N-Boc-protected [ 13 C]thiourea to afford N-Boc-protected [ 13 C]guanidine 6, which underwent base catalyzed ring opening. Removal of the N-Boc group afforded [guanido-13 C]-c-hydroxyarginine HCl salt 7 giving a 30% overall yield of the final product from N-Boc protected allylglycine 1 in five steps.

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“…Unsaturated a-amino acids can be considered useful chiral synthons 7 and important building blocks in the synthesis of biologically active peptides and peptides isosteres. 8 In particular, a-allyl-a-amino acids have been synthesised by alkylation of glycine and alanine synthons 9 or using chiral auxiliaries, 10 among other methods.…”

Section: Stereoselective Allylation Reactions Of Cis-and Trans-2-ferr...mentioning

confidence: 99%

Stereoselective functionalisation of cis- and trans-2-ferrocenyl-3-pivaloyl-4-alkyl-1,3-oxazolidin-5-ones: asymmetric synthesis of (R)- and (S)-2-alkyl-2-aminopent-4-enoic acids and (2R,3S)-2-amino-2-methyl-3-hydroxy-3-phenylpropanoic acid

et al. 2009

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Treatment of a range of cis- and trans-2-ferrocenyl-3-pivaloyl-4-alkyl-1,3-oxazolidin-5-ones with LDA followed by the addition of allyl bromide promotes highly stereoselective allylation (>98% de) at the 4-position of the oxazolidinone ring anti to the stereodirecting 2-ferrocenyl group. Hydrolysis of the resultant 4,4-disubstituted oxazolidinones (>98% de) yields enantiomeric (R)- and (S)-2-alkyl-2-aminopent-4-enoic acids in high ee. Furthermore, the aldol reaction of the lithium enolate of cis-2-ferrocenyl-3-pivaloyl-4-methyl-1,3-oxazolidin-5-one with benzaldehyde followed by in situ O-protection affords O-protected aldol products in >98% de, with hydrolysis affording (2R,3S)-2-amino-2-methyl-3-hydroxy-3-phenylpropanoic acid in >98% de.

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Enantioselective Synthesis of Epoxy Amino Acids

Cited by 12 publications

References 8 publications

Epoxy amino acids produced from allylglycines intramolecularly cyclised to yield four stereoisomers of 4-hydroxyproline derivatives

Epoxy amino acids produced from allylglycines intramolecularly cyclised to yield four stereoisomers of 4-hydroxyproline derivatives

Synthesis of [guanido‐¹³C]‐γ‐hydroxyarginine

Stereoselective functionalisation of cis- and trans-2-ferrocenyl-3-pivaloyl-4-alkyl-1,3-oxazolidin-5-ones: asymmetric synthesis of (R)- and (S)-2-alkyl-2-aminopent-4-enoic acids and (2R,3S)-2-amino-2-methyl-3-hydroxy-3-phenylpropanoic acid

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Enantioselective Synthesis of Epoxy Amino Acids

Cited by 12 publications

References 8 publications

Epoxy amino acids produced from allylglycines intramolecularly cyclised to yield four stereoisomers of 4-hydroxyproline derivatives

Epoxy amino acids produced from allylglycines intramolecularly cyclised to yield four stereoisomers of 4-hydroxyproline derivatives

Synthesis of [guanido‐13C]‐γ‐hydroxyarginine

Stereoselective functionalisation of cis- and trans-2-ferrocenyl-3-pivaloyl-4-alkyl-1,3-oxazolidin-5-ones: asymmetric synthesis of (R)- and (S)-2-alkyl-2-aminopent-4-enoic acids and (2R,3S)-2-amino-2-methyl-3-hydroxy-3-phenylpropanoic acid

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Synthesis of [guanido‐¹³C]‐γ‐hydroxyarginine