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33746604766
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For enopeptins, see
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For enopeptins, see: B. Hinzen, S. Raddatz, H. Paulsen, T. Lampe, A. Schumacher, D. H'bich, V. Hellwig, J. Benet-Buchholz, R. Endermann, H. Labischinski, H. Brötz-Oesterhelt, ChemMedChem 2006, 1, 689-693.
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HyGln is found in various non-ribosomal cyclopeptides, e.g.: a) neopeptins: M. Ubukata, M. Uramoto, J. Uzawa, K. Isono, Agric. Biol. Chem. 1986, 50, 357-365;
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38
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54849436453
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Attempts to selectively hydrolyze the C-terminal D-Orn methyl ester prior to cyclization exclusively yielded the undesired diacid (37→38). To solve this problem, we installed a trimethylsilylethyl (TMSE) ester as an (Chemical Equation Presented) additional dimension of protection at the D-Orn carboxylate. Boc deprotection had to be carried out cautiously due to the acid sensitivity of the TMSE group; now the complete N-deprotection of the indole ring could no longer be achieved with HCl (24→39). Still, the cyclization sequence could be done with the mono-Boc/bis-Boc mixture (40→32). (Chemical Equation Presented)
-
Attempts to selectively hydrolyze the C-terminal D-Orn methyl ester prior to cyclization exclusively yielded the undesired diacid (37→38). To solve this problem, we installed a trimethylsilylethyl (TMSE) ester as an (Chemical Equation Presented) additional dimension of protection at the D-Orn carboxylate. Boc deprotection had to be carried out cautiously due to the acid sensitivity of the TMSE group; now the complete N-deprotection of the indole ring could no longer be achieved with HCl (24→39). Still, the cyclization sequence could be done with the mono-Boc/bis-Boc mixture (40→32). (Chemical Equation Presented)
-
-
-
-
70
-
-
54849422431
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2, 80%]. EDC=1-ethyl-3-(3- dimethylaminopropyl)carbodiimide, Pfp=pentafluorophenyl.
-
2, 80%]. EDC=1-ethyl-3-(3- dimethylaminopropyl)carbodiimide, Pfp=pentafluorophenyl.
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71
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0028926676
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Genes AcrA and AcrB encode a stress-induced efflux system of Escherichia coli: D. Ma, D. N. Cook, M. Alberti, N. G. Pon, H. Nikaido, J. E. Hearst, Mol. Microbiol. 1995, 16, 45-55.
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Genes AcrA and AcrB encode a stress-induced efflux system of Escherichia coli: D. Ma, D. N. Cook, M. Alberti, N. G. Pon, H. Nikaido, J. E. Hearst, Mol. Microbiol. 1995, 16, 45-55.
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72
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[7] hydrolyzed the S-520 complex with 6N HCl at 105°C. Under these conditions, HyGln would have been transformed into HyGlu, the amino acid detected in the hydrolysate.
-
[7] hydrolyzed the "S-520 complex" with 6N HCl at 105°C. Under these conditions, HyGln would have been transformed into HyGlu, the amino acid detected in the hydrolysate.
-
-
-
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73
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0022969409
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For further asymmetric syntheses of HyGln derivatives, see: a
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For further asymmetric syntheses of HyGln derivatives, see: a) S. Cardani, L. Prati, O. Tinti, Synthesis 1986, 1032-1035;
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Cardani, S.1
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54849410465
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20=+13.2° (c=0.46, MeOH) [would correspond to +12.1° for the TFA salt].
-
20=+13.2° (c=0.46, MeOH) [would correspond to +12.1° for the TFA salt].
-
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80
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54849410845
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