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 2224024ノート

反応式

HRID 2224024 の反応式
[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]

参加物

3

反応物 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

生成物 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 ester収率 70.7%

試薬・触媒・溶媒 1

HCID 22185937THF TFA water溶媒

実験手順

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)+.

後処理

  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)

出典と根拠

ORDレコード
ord-96b5781e245141c2a85193b49e927705
出典データセット
uspto-grants-2008_05
特許番号
US07378410B2

反応ノート

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