A Fragmentational Approach to Macrolides: (5‐<i>E</i>, 8‐<i>Z</i>)‐6‐methyl‐5,8‐undecadien‐11‐olide

Sternbach, Daniel D.; Jaisli, Fritz; Bonetti, Marco; Eschenmoser, Albert; Shibuya, Masayuki

doi:10.1002/anie.197906341

Cited by 36 publications

(8 citation statements)

References 28 publications

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“…The origin of syn selectivity for nucleophilic approach is then attributed to more effective interaction with the C−H bond compared to C−F bond. The proposal has similarities to Eschenmoser and Grob fragmentations (Scheme ) which also involve rupture of several antiperiplanar bonds. The high degree of alignment of the participating bond orbitals is therefore the stringent requirement of the double hyperconjugation model.…”

Section: Orbital Effectsmentioning

confidence: 60%

Electronic Control of Facial Selection in Additions to Sterically Unbiased Ketones and Olefins

Mehta

Chandrasekhar

1999

Chem. Rev.

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Section: Orbital Effectsmentioning

confidence: 60%

Electronic Control of Facial Selection in Additions to Sterically Unbiased Ketones and Olefins

Mehta

Chandrasekhar

1999

Chem. Rev.

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“…1 Previous extended heterolytic fragmentations. [26][27][28] Scheme 2 Divergent fragmentation pathways of 1.…”

Section: Methodsmentioning

confidence: 99%

“…1a and b. [26][27][28] Highlighted in bold are the bonds involved in each fragmentation. Here we focus on designing systems where these sorts of cage-supported extended fragmentations can have divergent outcomes ( Fig.…”

Section: Introductionmentioning

confidence: 99%

Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations

2020

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“…Inspired by investigations of the Matile group on the importance of polyion‐counter‐ion complexes for cell penetration and remembering the perfect fit between guanidinium groups and so‐called oxy‐anions ( Figure ,a ) that had been used in organic synthesis and in supramolecular chemistry, we had prepared the 1:4 salt 1a ‐4 Fos of octaarginine amide and fosmidomycin to test its in vitro activity against P. falciparum , and we were able to report in 2013 that growth of this parasite (which causes malaria) was much more strongly reduced by the salt than by fosmidomycin itself ( Figure ,b and c ) …”

Section: Introductionmentioning

confidence: 99%

Cell Penetration, Herbicidal Activity, and in‐vivo‐Toxicity of Oligo‐Arginine Derivatives and of Novel Guanidinium‐Rich Compounds Derived from the Biopolymer Cyanophycin

Grogg

Hilvert

Ebert

et al. 2018

Helvetica Chimica Acta

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Oligo-arginines are thoroughly studied cell-penetrating peptides (CPPs, Figures 1 and 2). Previous in-vitro investigations with the octaarginine salt of the phosphonate fosmidomycin (herbicide and anti-malaria drug) have shown a 40-fold parasitaemia inhibition with P. falciparum, compared to fosmidomycin alone (Figure 3). We have now tested this salt, as well as the corresponding phosphinate salt of the herbicide glufosinate, for herbicidal activity with whole plants by spray application, hoping for increased activities, i.e. decreased doses. However, both salts showed low herbicidal activity, indicating poor foliar uptake (Table 1). Another pronounced difference between in-vitro and in-vivo activity was demonstrated with various cell-penetrating octaarginine salts of fosmidomycin: intravenous injection to mice caused exitus of the animals within minutes, even at doses as low as 1.4 μmol/kg (Table 2). The results show that use of CPPs for drug delivery, for instance to cancer cells and tissues, must be considered with due care. The biopolymer cyanophycin is a poly-aspartic acid containing argininylated side chains (Figure 4); its building block is the dipeptide H-βAsp-αArg-OH (H-Adp-OH). To test and compare the biological properties with those of octaarginines we synthesized Adp8-derivatives (Figure 5). Intravenouse injection of H-Adp8-NH2 into the tail vein of mice with doses as high as 45 μmol/kg causes no symptoms whatsoever (Table 3), but H-Adp8-NH2 is not cell penetrating (HEK293 and MCF-7 cells, Figure 6). On the other hand, the fluorescently labeled octamers FAM-(Adp(OMe))8-NH2 and FAM-(Adp(NMe2))8-NH2 with ester and amide groups in the side chains exhibit mediocre to high cell-wall permeability (Figure 6), and are toxic (Table 3). Possible reasons for this behavior are discussed (Figure 7) and corresponding NMR spectra are presented (Figure 8).

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A Fragmentational Approach to Macrolides: (5‐E, 8‐Z)‐6‐methyl‐5,8‐undecadien‐11‐olide

Cited by 36 publications

References 28 publications

Electronic Control of Facial Selection in Additions to Sterically Unbiased Ketones and Olefins

Electronic Control of Facial Selection in Additions to Sterically Unbiased Ketones and Olefins

Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations

Cell Penetration, Herbicidal Activity, and in‐vivo‐Toxicity of Oligo‐Arginine Derivatives and of Novel Guanidinium‐Rich Compounds Derived from the Biopolymer Cyanophycin

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