Vancomycin and ristocetin models: synthesis via the Ullmann macrocyclization reaction

Boger, Dale L.; Nomoto, Yuji; Teegarden, Bradley R.

doi:10.1021/jo00058a024

Cited by 83 publications

(42 citation statements)

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“…It must be noted that similar results were reported using other copper-based MOF materials, like Cu2(BDC)2(DABCO), being the best NB/Ph molar ratio 1/1.5 [20]. This result can be explained by the role of phenol as a ligand in the catalytic mechanism, which accelerates the coupling with aryl halides, as observed in homogeneous copper catalytic systems [26]. In the case of heterogeneous Cu-MOF materials, the benefit of using phenol in excess is also probably related to the primary interaction of phenolates with available copper sites followed by coupling with NB, instead of complexation of NB as electrophilic reactant and later coupling with phenolate as nucleophilic agent.…”

Section: Influence Of Temperaturesupporting

confidence: 81%

Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

Leo¹,

Orcajo²,

Briones³

et al. 2017

Preprint

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Abstract:The activity and cyclability of Cu-MOF-74 as catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration and basic agent (type and concentration) were evaluated. High conversions were achieved at 120°C, 5 mol% of catalyst, NB/Ph ratio of 1:2, DMF as solvent and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst.

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Section: Influence Of Temperaturesupporting

confidence: 81%

Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

Leo¹,

Orcajo²,

Briones³

et al. 2017

Preprint

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“…These salt-free conditions led to N-H bassianolide but in only 11% yield. In their synthesis of N-H bassianolide, Suzuki and coworkers attributed the low yield (2.8%) of their macrolactamization (PCl 5 and Et 3 N) to 3 10 -helical intramolecular hydrogen bonding (57,58) in their amino acid octadepsipeptide precursor (59). As a substrate for Mitsunobu esterification, 20 is a more hindered alcohol than 13.…”

Section: Significancementioning

confidence: 99%

Rapid synthesis of cyclic oligomeric depsipeptides with positional, stereochemical, and macrocycle size distribution control

Batiste

Johnston

2016

Proc. Natl. Acad. Sci. U.S.A.

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Macrocyclic small molecules are attractive tools in the development of sensors, new materials, and therapeutics. Within early-stage drug discovery, they are increasingly sought for their potential to interact with broad surfaces of peptidic receptors rather than within their narrow folds and pockets. Cyclization of linear small molecule precursors is a straightforward strategy to constrain conformationally mobile motifs, but forging a macrocycle bond typically becomes more difficult at larger ring sizes. We report the development of a general approach to discrete collections of oligomeric macrocyclic depsipeptides using an oligomerization/macrocyclization process governed by a series of Mitsunobu reactions of hydroxy acid monomers. Ring sizes of 18, 24, 30, and 36 are formed in a single reaction from a didepsipeptide, whereas sizes of 24, 36, and 60 result from a tetradepsipeptide. The ring-size selectivity inherent to the approach can be modulated by salt additives that enhance the formation of specific ring sizes. Use of chemical synthesis to prepare the monomers suggests broad access to functionally and stereochemically diverse collections of natural product-like oligodepsipeptide macrocycles. Two cyclodepsipeptide natural products were prepared along with numerous unnatural oligomeric congeners to provide rapid access to discrete collections of complex macrocyclic small molecules from medium (18) to large (60) ring sizes.Mitsunobu | total synthesis | collective | macrocycle | oligomerization I nterest in the preparation and use of small molecules exhibiting macrocyclic rings is growing at a tremendous pace, driving the development of new approaches, new chemical reactions, and the underlying chemistry and tools (catalysts) to support them. Historically, studies of macrocyclization reactions have been guided by natural products bearing unusually large carbocycles or mediumand large-ring lactones, amides, and ethers. Fragmentation reactions of polycyclic molecules have long played a role in access to medium-sized macrocycles, whereas macrocyclizations to lactones and amides are often accomplished from linear precursors at high dilution. Insofar as these efforts were typically driven by the goal to prepare a specific macrocycle, often in the form relevant to a natural product synthesis or an engineered constraint to a peptide, absent from the field is an approach that provides rapid access to collections (1) of natural product-like macrocycles, particularly from stereochemically complex, functionally rich, linear precursors (2-6).Pioneers in this area have recorded some success (Fig. 1). Esterification reactions of activated hydroxy acids have led predominantly to diolides, (7-10) and in a single case, oligolides (11). Amidation reactions of activated polypeptides were central to the preparations of macrocyclic peptides by Rothe and Kreiss (12,13) and Wipf and coworkers (14, 15), but they were low yielding and size nonselective. Burke and coworkers (16,17) have shown that the efficiency of an 18-membered oligol...

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“…This protocol helped realize the total synthesis of bouvardin (136), [141] combretastatin D 2, [221] deoxybouvardin (137), [206a, d] piperazinomycin (134, Figure 13), [220] and RA VII. [252] Buchwald and co-workers have also investigated coppermediated generation of bisaryl ethers. [253] Thus, by utilizing a stoichiometric amount of cesium carbonate they were able to couple unactivated aryl halides with phenols in the presence of a (CuOTf) 2´P hH catalyst (Scheme 56).…”

Section: The Classical Ullmann Reaction In Bisaryl Ether Synthesismentioning

confidence: 99%

Chemistry, Biology, and Medicine of the Glycopeptide Antibiotics

Nicolaou

Boddy

Bräse³

et al. 1999

Angew. Chem. Int. Ed.

719

445

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The war against infectious bacteria is not over! Although vancomycin and glycopeptide antibiotics have provided a strong last line of defence against many drug-resistant bacteria, their overuse has given rise to more dangerous strains of bacteria. An understanding of the chemistry and biology of these highly complex glycopeptides are destined to play a crucial role in the discovery of new antibiotics.

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Vancomycin and ristocetin models: synthesis via the Ullmann macrocyclization reaction

Cited by 83 publications

References 0 publications

Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

Rapid synthesis of cyclic oligomeric depsipeptides with positional, stereochemical, and macrocycle size distribution control

Chemistry, Biology, and Medicine of the Glycopeptide Antibiotics

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