4-Toluenesulfonyl chloride → HCID 11804060, compound

HRID 1827446Notes

Reaction equation

HRID 1827446 reaction equation
[CH2:1]([O:8][C@H:9]1[C@@:13]([CH2:16][O:17][C:18]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)([C:27]2[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][CH:28]=2)[C:19]2[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=2)([CH2:14][OH:15])[O:12][C@@H:11]([N:41]2[CH:49]=[C:47]([CH3:48])[C:45](=[O:46])[NH:44][C:42]2=[O:43])[C@@H:10]1[OH:50])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:51]1([CH3:61])[CH:56]=[CH:55][C:54]([S:57](Cl)(=[O:59])=[O:58])=[CH:53][CH:52]=1>N1C=CC=CC=1.CN(C1C=CN=CC=1)C>[CH2:1]([O:8][C@H:9]1[C@@:13]([CH2:16][O:17][C:18]([C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)([C:27]2[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][CH:28]=2)[C:19]2[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=2)([CH2:14][O:15][S:57]([C:54]2[CH:55]=[CH:56][C:51]([CH3:61])=[CH:52][CH:53]=2)(=[O:59])=[O:58])[O:12][C@@H:11]([N:41]2[CH:49]=[C:47]([CH3:48])[C:45](=[O:46])[NH:44][C:42]2=[O:43])[C@@H:10]1[O:50][S:57]([C:54]1[CH:55]=[CH:56][C:51]([CH3:61])=[CH:52][CH:53]=1)(=[O:59])=[O:58])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 73974-Toluenesulfonyl chlorideHCID 118026771(3-O-Benzyl-4-C-(4,4'-dimethoxytrityloxymethyl)-beta-D-xylofuranosyl)thymine

Product 1

HCID 11804060HCID 11804060, compoundYield 62.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

To a solution of nucleoside 6 (2.79 g, 3.9 mmol) in anhydrous pyridine (50 cm3) was added a catalytic amount of 4-(N,N-dimethylamino)pyridine and p-toluenesulphonyl chloride (6.50 g, 34 mmol). The mixture was stirred in the dark for 24 h at room temperature under nitrogen. The reaction was quenched by addition of a saturated aqueous solution of sodium hydrogen carbonate (100 cm3) and the resulting mixture was extracted with dichloromethane. The combined organic phase was washed with saturated aqueous solutions of sodium hydrogen carbonate (3×75 cm3) and sodium chloride (2×75 cm3). The separated organic phase was dried (Na2SO4) and evaporated to dryness under reduced pressure. The residue was purified by silica gel column chromatography using dichloromethane/methanol/pyridine (0.5% methanol; 0.5% pyridine, v/v) as eluent to afford nucteoside 7 (2.40 g, 62%) as a yellowish foam after evaporation of the solvents. δC ((CD3)2SO) 163.2 (C-4), 158.2, 145.9, 145.1, 144.3, 136.8, 135.0, 134.9, 134.8, 131.8, 131.6, 130.2, 130.0, 129.7, 128.2, 127.9, 127.8, 127.6, 127.5, 127.5, 127.4, 126.8, 113.3 (DMT, C-6, 2×Ts, benzyl), 150.2 (C-2), 110.8 (C-5), 95.0, 86.2 (DMT, C-4′), 82.2, 81.9 (C-1′, C-2′), 81.2 (C-3′), 72.9 (CH2Ph), 79 (C-5″), 64 (C-5′), 55.1 (2×CH3O), 21.2, 21.2 (2×CH3), 12.0 (5-CH3).

Workup

  1. customThe reaction was quenched by addition of a saturated aqueous solution of sodium hydrogen carbonate (100 cm3)
  2. extractionthe resulting mixture was extracted with dichloromethane
  3. washThe combined organic phase was washed with saturated aqueous solutions of sodium hydrogen carbonate (3×75 cm3) and sodium chloride (2×75 cm3)
  4. dry with materialThe separated organic phase was dried (Na2SO4)
  5. customevaporated to dryness under reduced pressure
  6. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-940cdf7aad7947848e023892b7ba7d5b
Source dataset
uspto-grants-2006_05
Patent number
US07053207B2

Reaction notes

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