Chlorotrimethylsilane → HCID 15126108、化合物

HRID 653981

反応式

HRID 653981 の反応式
C(O[CH:5]1[S:9][C@H:8]([CH2:10][O:11][Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:7][CH2:6]1)(=O)C.[NH:29]1[CH:36]=[CH:35][C:33]([NH2:34])=[N:32][C:30]1=[O:31].FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S([O-])(=O)=O.[K+].C[Si](N[Si](C)(C)C)(C)C.[Si](Cl)(C)(C)C.C([O-])(O)=O.[Na+]>C(#N)C.ClCCl>[Si:12]([O:11][CH2:10][C@H:8]1[S:9][C@@H:5]([N:29]2[CH:36]=[CH:35][C:33]([NH2:34])=[N:32][C:30]2=[O:31])[CH2:6][CH2:7]1)([C:25]([CH3:27])([CH3:26])[CH3:28])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

参加物

9

反応物 6

HCID 6397ChlorotrimethylsilaneHCID 13838HexamethyldisilazaneHCID 516892Sodium BicarbonateHCID 151260981-O-Acetyl-5-O-t-butyldiphenylsilyl-4-thio-2,3-dideoxyribofuranoseHCID 23675274Potassium perfluorobutanesulfonateHCID 178418229Cytosine

生成物 1

HCID 15126108HCID 15126108、化合物

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
25 °C

実験手順

A mixture of 10 (0.26 g, 0.63 mmol), cytosine (0.105 g, 0.95 mmol), and potassium nonafluorobutanesulfonate (0.77 g, 2.3 mmol) was suspended in 12 mL dry acetonitrile under nitrogen. HMDS (0.135 mL, 0.63 mmol) and TMS-Cl (0.37 mL, 2.9 mmol) were added sequentially via syringe and the reaction stirred at 25° C. overnight. The reaction was poured into a mixture of 20 mL dichloromethane and 15 mL saturated NaHCO3 and shaken. The organic phase was dried (MgSO4) and concentrated in vacuo. The anomeric mixture was separated by preparative TLC with 7.5% MeOH/CHCl3 with an ammonia atmosphere: yield of β-anomer, 78 mg and 117 mg of the α-anomer to afford total yield of 195 mg (66.5%); FAB MS 466 (M+H)+ ; 1H NMR (CDCl3) of α/β anomer, δ 8.12 (d, 1, 6-H), 7.7 (m, 4, ArH), 7.4 (m, 6, ArH), 6.32 (m, 1, 1'-H), 5.9-5.3 (hump, 1, NH2), 5.75 (d, 1, 5-H), 5.45 (d, 1, 5-H), 3.75 (m, 3, 4'-Hα,β 's, 3'-Hα,β 's).

後処理

  1. stirringshaken
  2. dry with materialThe organic phase was dried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customThe anomeric mixture was separated by preparative TLC with 7.5% MeOH/CHCl3 with an ammonia atmosphere
  5. customyield of β-anomer, 78 mg and 117 mg of the α-anomer to afford total yield of 195 mg (66.5%)

出典と根拠

ORDレコード
ord-e369a01e7e4949d5a42ef03f07094859
出典データセット
uspto-grants-1992_07
特許番号
US05128458

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