Trimethylsilyl triflate → Phenyl 2-o-acetyl-3,5-di-o-benzyl-4-c-methanesulfonyloxymethyl-1-thio-beta-d-ribofuranoside

HRID 659873

반응식

HRID 659873 반응식
[C:1]([O:4][C@@H:5]1[C@H:11]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C@@:10]([CH2:29][O:30][S:31]([CH3:34])(=[O:33])=[O:32])([CH2:20][O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[O:9][CH:6]1OC)(=[O:3])[CH3:2].[C:35]1([S:41][Si](C)(C)C)[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.O([Si](C)(C)C)S(C(F)(F)F)(=O)=O>ClCCl>[C:1]([O:4][C@@H:5]1[C@H:11]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C@@:10]([CH2:29][O:30][S:31]([CH3:34])(=[O:33])=[O:32])([CH2:20][O:21][CH2:22][C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[O:9][C@H:6]1[S:41][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)(=[O:3])[CH3:2]

참가 물질

5

반응물 3

HCID 65367Trimethylsilyl triflateHCID 78312PhenylthiotrimethylsilaneHCID 11145450Methyl 2-O-acetyl-3,5-di-O-benzyl-4-C-methanesulfonyloxymethyl-D-ribofuranoside

생성물 1

HCID 10940817Phenyl 2-o-acetyl-3,5-di-o-benzyl-4-c-methanesulfonyloxymethyl-1-thio-beta-d-ribofuranoside수율 66.1%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

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온도
0 °C

실험 절차

Method a. A stirred solution of 209 (738 mg, 1.49 mmol) in anhydrous dichloromethane (6.4 mL) was added phenylthiotrimethylsilane (2.42 mL, 12.8 mmol) and cooled to 0° C. Trimethylsilyl triflate (0.67 mL, 3.67 mmol) was added dropwise and the solution was stirred at room temperature for 4 h. The reaction was quenched with a saturated aqueous solution of sodium hydrogen carbonate (100 mL) and extracted with dichloromethane (2×200 mL). The combined extract was dried (MgSO4) and the solvent removed by distillation under reduced pressure. The residue was purified by chromatography over silica gel with dichloromethane as eluent to give the product 210 as a clear oil (564 mg, 66%) and unreacted starting material (191 mg, 26%); Method b. A stirred solution of 211 (86 mg, 0.165 mmol) in anhydrous dichloromethane (0.49 mL) was added phenylthiotrimethylsilane (0.16 mL, 0.825 mmol) and cooled to 0° C. Trimethylsilyl triflate (0.037 mL, 0.206 mmol) was added and the solution was stirred at room temperature for 2 h. The reaction was quenched with a saturated aqueous solution of sodium hydrogen carbonate (15 mL) and the resulting mixture was extracted with dichloromethane (2×25 mL). The combined extract was dried (MgSO4) and the solvent removed by distillation under reduced pressure. The residue was purified by chromatography over silica gel with dichloromethane as eluent to give the product 210 as a clear oil (75 mg, 79%); 1H NMR (CDCl3): δ 7.47-7.19 (15H, m, Bn, SPh), 5.48 (1H, d, J 3.6 Hz, H-2), 5.34 (1H, dd, J 3.7, 5.2 Hz, H-1), 4.54-4.36 (7H, m, H-3, H-5□, Bn), 3.66 (1H, d, J 9.7 Hz, H-5), 3.48 (1H, d, J 9.5 Hz, H-5), 2.89 (3H, s, SO2CH3), 2.09 (3H, s, OCCH3); 13C NMR (CDCl3): δ 169.93 (C═O), 137.69, 137.08, 132.65, 132.45, 129.15, 128.53, 128.52, 128.18, 128.14, 128.08, 127.91, 127.85 (Bn, SPh), 87.99, 84.35, 80.34, 75.33, 74.20, 73.67, 70.83, 69.34 (C-1, C-2, C-3, C-4, C-5, C-5′, Bn), 37.27 (SO2CH3), 20.68 (OCCH3); MS FAB: 463 (M−SPh, 100%), 595 (M+Na, 24%). Found. C, 61.17; H, 5.55; C29H32O8S2 requires C, 60.82; H, 5.63%.

후처리

  1. customThe reaction was quenched with a saturated aqueous solution of sodium hydrogen carbonate (100 mL)
  2. extractionextracted with dichloromethane (2×200 mL)
  3. extractionThe combined extract
  4. dry with materialwas dried (MgSO4)
  5. customthe solvent removed by distillation under reduced pressure
  6. customThe residue was purified by chromatography over silica gel with dichloromethane as eluent

출처 및 근거

ORD 기록
ord-7c84f743ee4a4ba297ed4ecbfd7bb6d9
출처 데이터셋
uspto-grants-2011_12
특허 번호
US08080644B2

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