Synthesis of terminally protected (S)-β3-H-DOPA by Arndt–Eistert homologation: an approach to crowned β-peptides

Gaucher, Anne; Dutot, Laurence; Barbeau, Olivier; Hamchaoui, Wahib; Wakselman, Michel; Mazaleyrat, Jean‐Paul

doi:10.1016/j.tetasy.2004.11.089

Cited by 29 publications

(27 citation statements)

References 36 publications

(13 reference statements)

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“…174-175°C (methanol/dichloromethane) (lit. : 172-174°C, [36] 170-171°C, [37] 170.5-171.5°C [38] [36,39,40] Triethylamine (0.0510 mol, 7.15 mL) and di-tert-butyl dicarbonate (11.1 g, 0.0510 mol) were added to ester 9 (12.5 g, 0.0505 mol) in methanol (275 mL) at room temperature. The solution was then stirred for 2 h. After completion (monitored by TLC, n-heptane/ethyl acetate, 5:5), the solvent was evaporated and the residue was acidified with 1  hydrochloric acid (50 mL) at 0°C.…”

Section: Methodsmentioning

confidence: 99%

“…134-135°C (methanol) {lit. : 133-135°C, [36] 140-141°C (methanol/water), [39] 135°C [40] }, R f = 0.3 (n-heptane/ethyl acetate, 5: [36] [α] D 25 = +7 (methanol, c = 1) [40] [41] Compound 10 (14 g, 0.045 mol) and methyl iodide (27.5 g, 0.202 mol) were added to a stirred solution of dimethylformamide (100 mL) and potassium carbonate (55.9 g, 0.405 mol). The mixture was then stirred for 24 h. Monitoring by TLC (n-heptane/ethyl acetate, 7:3) indicated the disappearance of the starting material.…”

Section: Methodsmentioning

confidence: 99%

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Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

2007

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Synthetic investigations of 1,3‐dichloro‐5,6‐dicyanobenzoquinone‐mediated benzylic oxidation is reported for the synthesis of natural alkaloid analogues. Extensive explorations of the oxidative nucleophilic substitution of the benzylic position of β‐phenylethylamine derivatives and the synthesis of functionalized tetrahydroisoquinolines of ecteinascidin 743 precursors have been carried out. Starting from L‐DOPA, a tunable oxazolidinone group was installed under oxidative benzylic conditions. This derivative 13 was submitted to benzylic oxidation reactions using a wide range of carboxylic acids and subsequent chemical transformations of these compounds were attempted. Moreover, an efficient synthesis of an aromatic ketone derivative 20 was achieved and gave rise to tetrahydroisoquinoline 24 through a direct Pictet–Spengler cyclisation reaction. Subsequently, 24 was transformed into functionalized α‐amino alcohols 31a and 31b, precursors of ecteinascidin 743 analogues. In addition, in order to assess the viability of our synthetic strategy, the reaction of 24 with methyl thioglycolate was performed and the stereoselectivity confirmed by X‐ray analysis of 33a. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

2007

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“…Then, hydrolysis of the methyl ester protecting group of compound 9 afforded the carboxylic acid of compound 10 (Scheme 5, step iv). It is well-known that hydrolysis of ester is under alkaline conditions which has a significant impact on the conformation of peptide [19,20,21,22,23,24]. However, the macrocyclization step is critical in the synthesis of cyclic peptide, and may depend on the peptide sequence, structural constraints, and the resulting ring [25,26,27].…”

Section: Resultsmentioning

confidence: 99%

A Practical and Total Synthesis of Pasireotide: Synthesis of Cyclic Hexapeptide via a Three-Component Condensation

Chen

Chu

et al. 2019

Molecules

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Pasireotide is a multi-receptor ligand somatostatin analogue approved for medical treatment of Cushing’s disease and acromegaly. The liquid-phase total synthesis of pasireotide-a 18-membered cyclic hexapeptide-was achieved by the 3 + 2 + 1 strategy, and the Pro1-Phe6 peptide bond was selected as the final cyclization position. Two key fragments were simply synthesized using N,O-bis(trimethylsilyl)acetamide/N-hydroxysuccinimide ester (BSA/NHS) as coupling agents, and processes of the two key fragments were simple without any chromatographic purification. The current synthesis method is easily scalable and produces the target peptide with an overall yield of 15%.

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“…The homologation pathway was carried out by using an Arndt-Eistert rearrangement, [17] and the ester 5 was obtained in moderate yield with total retention at C-4, a sole diastereomer being recovered from the reaction mixture.…”

Section: Resultsmentioning

confidence: 99%

A New Conformationally Restricted Mimetic of Dipeptide EG – Synthesis of an Analogue of FEG

et al. 2007

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Starting from the chiral pyrrolidin‐2‐one 2, the carboxy group at C‐4 underwent homologation, and subsequent removal of the 1‐(4‐methoxyphenyl)ethyl group gave lactam 6. Alkylation of N‐1 with benzyl bromoacetate led to 7, a new conformationally restricted analogue of the dipeptide EG (Glu‐Gly). The usefulness of 7 was demonstrated by its eventual conversion into 8, an orthogonally protected analogue ofbioactive tripeptide FEG. In order to provide the biological activity of the new mimetic 9, available from 8 after the removal of the protecting groups, the conformational preference of 9 was ascertained by a detailed conformational analysis and a comparison with that of FEG (1). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Synthesis of terminally protected (S)-β3-H-DOPA by Arndt–Eistert homologation: an approach to crowned β-peptides

Cited by 29 publications

References 36 publications

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

A Practical and Total Synthesis of Pasireotide: Synthesis of Cyclic Hexapeptide via a Three-Component Condensation

A New Conformationally Restricted Mimetic of Dipeptide EG – Synthesis of an Analogue of FEG

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Synthesis of terminally protected (S)-β3-H-DOPA by Arndt–Eistert homologation: an approach to crowned β-peptides

Cited by 29 publications

References 36 publications

Oxidative Nucleophilic Substitution (SNOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Oxidative Nucleophilic Substitution (SNOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

A Practical and Total Synthesis of Pasireotide: Synthesis of Cyclic Hexapeptide via a Three-Component Condensation

A New Conformationally Restricted Mimetic of Dipeptide EG – Synthesis of an Analogue of FEG

Contact Info

Product

Resources

About

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues

Oxidative Nucleophilic Substitution (S_NOx) of the Benzylic Position as a Tunable Synthesis of Tetrahydroisoquinoline Natural Alkaloid Analogues