Synthesis of the Rubiyunnanin B Core Aglycon

Moschitto, Matthew J.; Lewis, Chad A.

doi:10.1002/ejoc.201600741

Cited by 9 publications

(7 citation statements)

References 25 publications

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“…Treating the Boc-protected methyl ester of iodotyrosine 21 with a larger excess of base and methyl iodide (10 equiv each) led to the formation of the α-quaternary amino acid 23 (Scheme 4). An alternative route to the N -methylated product via oxazolidinone 24 was hampered by low yield on reaction with paraformaldehyde [47–48]. Although subsequent reduction of 24 with Et 3 SiH/TFA and reprotection of the free N -methyl amino acid with Boc 2 O proceeded smoothly and delivered iodotyrosine 25 , the overall yield via 24 was not satisfying.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of the polyketide section of seragamide A and related cyclodepsipeptides via Negishi cross coupling

Lang¹,

Lindel²

2019

Beilstein J. Org. Chem.

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The synthesis of the polyketide section present in the potently cytotoxic marine cyclodepsipeptide jasplakinolide and related natural products, geodiamolides and seragamides, is reported. The key step is a Negishi cross coupling of (R)-(3-methoxy-2-methyl-3-oxopropyl)zinc(II) bromide and an (E)-iodoalkene that was synthesized via an aluminium ester enolate attack at (R)-propylene oxide. The overall synthesis comprises nine steps with an overall yield of 21%. It proved to be possible to liberate the free 8-hydroxynonenoic acid and to couple it with a protected tripeptide composed of L-alanine, N,O-dimethyl-D-iodotyrosine, and TIPS-protected L-threonine, which occurs as partial structure of seragamide A. The tripeptide section of seragamide A was assembled by solution-phase synthesis and an open-chain analogue of the natural product was obtained.

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Section: Resultsmentioning

confidence: 99%

Synthesis of the polyketide section of seragamide A and related cyclodepsipeptides via Negishi cross coupling

Lang¹,

Lindel²

2019

Beilstein J. Org. Chem.

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“…12,16 Carboxybenzyl (Cbz) protected iodotyrosines 3 have also been previously accessed. 17,18 While these can be used in solution phase synthesis the aforementioned combination of protecting groups are not compatible with fluorenylmethyloxycarbonyl (Fmoc) based solid phase peptide (SPPS) synthesis. For example, 1 and 2 could only be incorporated at the N-terminus of an Fmoc SPPS-synthesised peptide sequence and in the case of 2 additional steps would be required to remove the methyl ether after peptide cleavage from the solid support.…”

Section: Graphical Abstractmentioning

confidence: 99%

A direct route for the preparation of Fmoc/O Bu protected iodotyrosine

Steer

Bolt

Brittain

et al. 2018

Tetrahedron Letters

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“…The cyclization was then performed by lactamization, to again provide 108. Owing to their widespread occurrence in nature [61] and the efficient access of biaryl-bridged peptides via Suzuki-Miyaura cross-couplings, multiple research teams focused their efforts on natural product synthesis of, among others, TMC-95A/B 109a,b [164][165][166][167][168], arylomycins 110a,b [169], complestatin [170,171] and Rubiyunnanin B [172], wherein the Suzuki-Miyaura reaction often serves as the disconnection site of the biaryl-bridge ( Figure 15C). …”

Section: Formation Of Biaryl-bridges In Peptidic Natural Products Andmentioning

confidence: 99%

“…[61] and the efficient access of biaryl-bridged peptides via Suzuki-Miyaura cross-couplings, multiple research teams focused their efforts on natural product synthesis of, among others, TMC-95A/B 109a,b [164][165][166][167][168], arylomycins 110a,b [169], complestatin [170,171] and Rubiyunnanin B [172], wherein the Suzuki-Miyaura reaction often serves as the disconnection site of the biaryl-bridge ( Figure 15C). Afonso et al extended their work on cross-couplings of borylated peptides on solid support [158] through the cyclization of a linear peptide, for example, 111, containing both the boronate and the halogenated aromatic amino acid [120].…”

Section: Formation Of Biaryl-bridges In Peptidic Natural Products Andmentioning

confidence: 99%

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

et al. 2017

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Abstract:The (site-selective) derivatization of amino acids and peptides represents an attractive field with potential applications in the establishment of structure-activity relationships and labeling of bioactive compounds. In this respect, bioorthogonal cross-coupling reactions provide valuable means for ready access to peptide analogues with diversified structure and function. Due to the complex and chiral nature of peptides, mild reaction conditions are preferred; hence, a suitable cross-coupling reaction is required for the chemical modification of these challenging substrates. The Suzuki reaction, involving organoboron species, is appropriate given the stability and environmentally benign nature of these reactants and their amenability to be applied in (partial) aqueous reaction conditions, an expected requirement upon the derivatization of peptides. Concerning the halogenated reaction partner, residues bearing halogen moieties can either be introduced directly as halogenated amino acids during solid-phase peptide synthesis (SPPS) or genetically encoded into larger proteins. A reversed approach building in boron in the peptidic backbone is also possible. Furthermore, based on this complementarity, cyclic peptides can be prepared by halogenation, and borylation of two amino acid side chains present within the same peptidic substrate. Here, the Suzuki-Miyaura reaction is a tool to induce the desired cyclization. In this review, we discuss diverse amino acid and peptide-based applications explored by means of this extremely versatile cross-coupling reaction. With the advent of peptide-based drugs, versatile bioorthogonal conversions on these substrates have become highly valuable.

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Synthesis of the Rubiyunnanin B Core Aglycon

Cited by 9 publications

References 25 publications

Synthesis of the polyketide section of seragamide A and related cyclodepsipeptides via Negishi cross coupling

Synthesis of the polyketide section of seragamide A and related cyclodepsipeptides via Negishi cross coupling

A direct route for the preparation of Fmoc/O Bu protected iodotyrosine

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

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