tetradecanoic acid (3R,6S)-6-{(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetylamino}-7-oxo-1-pyridin-3-ylmethyl-azepan-3-yl ester → tetradecanoic acid (3R,6S)-7-oxo-1-pyridin-3-ylmethyl-6-((2R,3R,4S,5R)-(E)-3,4,5-trihydroxy-2-methoxy-8,8-dimethyl-non-6-enoylamino)-azepan-3-yl ester

HRID 2224024Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2224024
[CH3:1][C:2]([CH3:52])([CH3:51])/[CH:3]=[CH:4]/[C@H:5]1[O:10]C(C)(C)[O:8][C@@H:7]([C@@H:13]([O:48][CH3:49])[C:14]([NH:16][C@@H:17]2[C:23](=[O:24])[N:22]([CH2:25][C:26]3[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=3)[CH2:21][C@H:20]([O:32][C:33](=[O:47])[CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46])[CH2:19][CH2:18]2)=[O:15])[C@@H:6]1[OH:50]>C(O)(C(F)(F)F)=O.C1COCC1.O>[O:24]=[C:23]1[N:22]([CH2:25][C:26]2[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=2)[CH2:21][C@H:20]([O:32][C:33](=[O:47])[CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46])[CH2:19][CH2:18][C@@H:17]1[NH:16][C:14](=[O:15])[C@H:13]([O:48][CH3:49])[C@H:7]([OH:8])[C@@H:6]([OH:50])[C@H:5]([OH:10])/[CH:4]=[CH:3]/[C:2]([CH3:1])([CH3:51])[CH3:52]

Komponenten

3

Edukt 1

HCID 86609576tetradecanoic acid (3R,6S)-6-{(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetylamino}-7-oxo-1-pyridin-3-ylmethyl-azepan-3-yl ester

Produkt 1

HCID 59716389tetradecanoic acid (3R,6S)-7-oxo-1-pyridin-3-ylmethyl-6-((2R,3R,4S,5R)-(E)-3,4,5-trihydroxy-2-methoxy-8,8-dimethyl-non-6-enoylamino)-azepan-3-yl esterAusbeute 70,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 22185937THF TFA waterLösungsmittel

Versuchsvorschrift

To a solution of TFA/THF/H2O (3/3/2) (30 mL) at 0° C. is added tetradecanoic acid (3R,6S)-6-{(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetylamino}-7-oxo-1-pyridin-3-ylmethyl-azepan-3-yl ester (0.3 g, 0.42 mmol). After 30 min the reaction is evaporated under high vacuum, toluene is added (20 mL) and evaporated under high vacuum to remove remaining TFA. The residue is dissolved in CH2Cl2 at 0° C. and neutralized by adding NH4OH dropwise. The solution is concentrated and chromatographed on silica (98% CH2Cl2/2% CH3OH) to give 0.2 g (70.7%) of tetradecanoic acid (3R,6S)-7-oxo-1-pyridin-3-ylmethyl-6-((2R,3R,4S,5R)-(E)-3,4,5-trihydroxy-2-methoxy-8,8-dimethyl-non-6-enoylamino)-azepan-3-yl ester as a with solid. 1H NMR 300 MHz δ 8.62 (s, 2H), 8.17 (d, 1H), 7.67 (d, 1H), 7.33 (m, 1H), 5.83 (d, 1H), 5.42(dd, 1H), 4.69 (m, 1H), 4.54 (m, 1H), 4.33 (d, 1H), 4.32 (t, 1H), 3.83 (dd, 2H), 3.67 (d, 1H), 3.25 (s, 3H), 3.17 (m, 1H), 2.94 (d, 1H), 2.29 (t, 2H), 2.13 (m, 2H), 2.00 (m, 1H), 1.60 (m, 3H), 1.29 (m, 24H), 1.04 (s, 9H), 0.89 (t, 3H); MS (ESI) 690.3 (M+H)+.

Aufarbeitung

  1. customAfter 30 min the reaction is evaporated under high vacuum, toluene
  2. additionis added (20 mL)
  3. customevaporated under high vacuum
  4. customto remove
  5. dissolutionThe residue is dissolved in CH2Cl2 at 0° C.
  6. additionby adding NH4OH dropwise
  7. concentrationThe solution is concentrated
  8. customchromatographed on silica (98% CH2Cl2/2% CH3OH)

Quellen und Nachweise

ORD-Eintrag
ord-96b5781e245141c2a85193b49e927705
Quelldatensatz
uspto-grants-2008_05
Patentnummer
US07378410B2

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