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Cesium carbonate → 2-(2-Methoxycarbonylethylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

HRID 653323
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HRID 653323 반응식
[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:13]([O:19][C@H:20]2[O:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9]Br)(=[O:3])[CH3:2].[SH:48][CH2:49][CH2:50][C:51]([O:53][CH3:54])=[O:52].C(=O)([O-])[O-].[Cs+].[Cs+].C(OCC)(=O)C.C(CC(C)(C)C)(C)C>[Cl-].C[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C1C=CC=CC=1.O>[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:13]([O:19][C@H:20]2[O:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9][S:48][CH2:49][CH2:50][C:51]([O:53][CH3:54])=[O:52])(=[O:3])[CH3:2]
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반응물 4

HCID 10796Cesium carbonateHCID 18050Methyl 3-mercaptopropionate2회HCID 18516502EtOAc isooctaneHCID 228870902-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

생성물 1

HCID 54172652
2-(2-Methoxycarbonylethylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

시약·촉매·용매 3

HCID 21218Trioctylmethylammonium chloride촉매HCID 241Benzene용매HCID 962Water용매

실험 절차

2-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside (15) (251 mg; 0.338 mmol), methyl 3-mercaptopropionate (38 μl; 0.35 mmol) methyltrioctylammonium chloride (ca 10 mg) and cesium carbonate (114 mg; 0.35 mmol) were dissolved in benzene (0.5 ml) and water (0.5 ml). The reaction mixture was stirred (magnet) over night and analyzed by TLC (SiO2, ethyl acetate:isooctane 4:1; reaction 2/3 completed). Methyl 3-mercaptopropionate (ca 20 μl) was added and the reaction mixture was stirred for 24 h (TLC showed complete reaction). The phases were separated, the water phase was extracted twice with methylene chloride and the combined organic phases were dried (sodium sulfate) which gave a yellow to green solution. Evaporation gave a syrup which was chromatographed (SiO2, ethyl acetate:isooctane 2:1) to give the title compound (22) as a syrup. Yield: 211 mg (80%). [α]D23 +70.0° (c 0.6; CHCl3); 1H-NMR (CDCl3, TMS) δ 5.57 (d, 1H, J3',4' =3.0 Hz, H4'), 5.39 (dd, 1H, J2',3' =11.0 Hz. H2'), 5.19 (dd, 1H, H3'), 5.17 (dd, 1H, J2,3 =11 Hz, H2), 5.00 (d, 1H, J1',2' =4.0 Hz, H1'), 4.80 (dd, 1H, J3,4 =3.0 Hz, H3), 4.51 (d, 1H, J1,2 =8.0 Hz, H1), 3.70 (s, 3H, CH3 --O), 2.82, 2.75, 2.63 (t, 2H each, J=7 Hz, CH2 --S, CH2 --CO), 2.13, 2.11, 2.08, 2.08, 2.06, 2.04, 1.98 (s, 3H each, CH3CO) ppm. 13C-NMR (CDCl3, TMS) δ 172.3 (COOCH3), 170.7, 170.6, 170.5, 170.4, 170.1, 169.8, 169.2 (CH3CO), 101.1 (Cl), 99.4 (Cl'), 77.1, 72.7, 72.0, 68.6, 68.5, 67.9, 67.4, 67.1 (C2-C5, C2'-C5'), 69.5 (OCH2), 62.0, 60.5 (C6, C6'), 51.8 (COOCH3), 34.7, 31.4, 27.4 (CH2S, CH2 --CO), 21.0, 20.7 (CH3CO) ppm.

후처리

  1. stirringthe reaction mixture was stirred for 24 h
  2. custom(TLC showed complete reaction)
  3. customThe phases were separated
  4. extractionthe water phase was extracted twice with methylene chloride
  5. dry with materialthe combined organic phases were dried (sodium sulfate) which
  6. customgave a yellow to green solution
  7. customEvaporation
  8. customgave a syrup which
  9. customwas chromatographed (SiO2, ethyl acetate:isooctane 2:1)

출처 및 근거

ORD 기록
ord-36df67bfbe55479ca97689c189ee47e3
출처 데이터셋
uspto-grants-1987_06
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US04675392

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