Oxidative coupling of arylglycine-containing peptides. A biomimetic approach to the synthesis of the macrocyclic actinoidinic-containing vancomycin subunit

Evans, David A.; Dinsmore, Christopher J.; Evrard, Deborah A.; DeVries, Keith M.

doi:10.1021/ja00067a074

Cited by 117 publications

(49 citation statements)

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“…Because of the inherent propensity of 13 to cyclodimerize, we wondered if salt effects could make formation of the 24-membered (6) precursor to verticilide selective. Our previous experiments with didepsipeptide monomer 5 showed that this was possible to some extent when the yield of the 36-membered ring was doubled in the presence of KBF 4 .…”

Section: Significancementioning

confidence: 96%

“…Lithium salts are known chaotropes, and therefore, it is not surprising that they interacted with the ionic Mitsunobu intermediates at such a level that no reactivity was observed. However, a shift in the size distribution of macrocyclic products was observed in the presence of NaBF 4 , KBF 4 , and CsCl. In the presence of NaBF, KBF 4 , or CsCl, production of the 18-membered ring was completely suppressed.…”

Section: Significancementioning

confidence: 96%

“…However, a shift in the size distribution of macrocyclic products was observed in the presence of NaBF 4 , KBF 4 , and CsCl. In the presence of NaBF, KBF 4 , or CsCl, production of the 18-membered ring was completely suppressed. These three salts also provided increased amounts of 24-membered ring relative to 30-membered ring compared with providing them in nearly equal amounts without a salt additive.…”

Section: Significancementioning

confidence: 96%

“…Ring-size enhancement in the presence of a salt additive was most significant for the 36-membered ring, which was retrieved in 44% isolated yield with KBF 4 , nearly double the yield of salt-free conditions. Additionally, KBF 4 increased the overall isolated yield of macrocycles from 64 to 81% along with evidence that less material was converted into linear DIAD substrate acylation by-products. This type of by-product is common (52)(53)(54) in Mitsunobu reactions, especially in the presence of excess coupling reagents, which are generally required for a macrolactonization to occur.…”

Section: Significancementioning

confidence: 96%

“…Bromide, chloride, and tetrafluoroborate anions were chosen in particular based on their likelihood to remain inert in the reaction conditions, unlike other noncoordinating counterions (PF 6 − and ClO 4 − ), which are known to form stable and insoluble complexes with arylphosphonium cations (51). Compared with the standard conditions, use of LiBF 4 and LiBr additives arrested the production of any cyclodepsipeptide products. Lithium salts are known chaotropes, and therefore, it is not surprising that they interacted with the ionic Mitsunobu intermediates at such a level that no reactivity was observed.…”

Section: Significancementioning

confidence: 99%

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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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Section: Significancementioning

confidence: 96%

Section: Significancementioning

confidence: 96%

Section: Significancementioning

confidence: 96%

Section: Significancementioning

confidence: 96%

Section: Significancementioning

confidence: 99%

See 3 more Smart Citations

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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Totalsynthese des Vancomycin- und des Eremomycin-Aglycons

et al. 1998

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Die Kontrolle der Elemente planarer und axialer Chiralität ist die größte Herausforderung bei der Synthese des Aglycons von Vancomycin – Vancomycin ist der Prototyp einer Familie von Glycopeptid‐Antibiotika, die effektiv zur Behandlung von Infektionen durch das Methicillin‐resistente Bakterium Staphylococcus aureus eingesetzt werden. Die erste Totalsynthese des Vancomycin‐ und des Eremomycin‐Aglycons gibt Aufschluß über den Einfluß der Struktur auf die kinetische und thermodynamische Kontrolle der atropselektiven Makrocyclisierungen.

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Unkonventionelle stereochemische Fragestellungen bei der Planung der Synthese von Vancomycin-Antibiotika: Herausforderungen durch axial- und nicht-planar-chirale Elemente der Heptapeptid-Aglyconbausteine

et al. 1998

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Oxidative coupling of arylglycine-containing peptides. A biomimetic approach to the synthesis of the macrocyclic actinoidinic-containing vancomycin subunit

Cited by 117 publications

References 0 publications

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

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

Totalsynthese des Vancomycin- und des Eremomycin-Aglycons

Unkonventionelle stereochemische Fragestellungen bei der Planung der Synthese von Vancomycin-Antibiotika: Herausforderungen durch axial- und nicht-planar-chirale Elemente der Heptapeptid-Aglyconbausteine

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