Lithium Chloride → HCID 68159448, compound

HRID 341024Notes

Reaction equation

HRID 341024 reaction equation
[CH3:1][N:2]([CH3:24])[S:3]([N:6]1[CH:10]=[CH:9][N:8]=[C:7]1[Sn](CCCC)(CCCC)CCCC)(=[O:5])=[O:4].C1(C)C(C([O:33][C@@H:34]2[C@@H:38]([CH2:39][O:40]C(C3C(C)=CC=CC=3)=O)[O:37][C@@H:36]([N:50]3[C:54]4=[N:55][CH:56]=[CH:57][C:58](I)=[C:53]4[CH:52]=[CH:51]3)[CH2:35]2)=O)=CC=CC=1.[Cl-].[Li+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C@@H:36]1([N:50]2[C:54]3=[N:55][CH:56]=[CH:57][C:58]([C:7]4[N:6]([S:3]([N:2]([CH3:1])[CH3:24])(=[O:4])=[O:5])[CH:10]=[CH:9][N:8]=4)=[C:53]3[CH:52]=[CH:51]2)[O:37][C@H:38]([CH2:39][OH:40])[C@@H:34]([OH:33])[CH2:35]1

Participants

6

Reactant 3

HCID 433294Lithium ChlorideHCID 70243600HCID 70243600, compoundHCID 131731282HCID 131731282, compound

Product 1

HCID 68159448HCID 68159448, compoundYield 54%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

N-Dimethylaminosulfonyl-2-(tributylstannyl)imidazole (930 mg, 2.0 mmol) was added to a solution of 1-[2-deoxy-3,5-di-O-(toluoyl)-β-D-ribofuranosyl]-4-iodo-pyrrolo[2,3-b]pyridine (596 mg, 1.0 mmol), lithium chloride (42 mg, 1.0 mmol), and tetrakis(triphenylphosphine)palladium (58 mg, 0.05 mmol) in dioxane (10 mL), followed by stirring at 120° C. for 4 hr. The reaction solution was concentrated and was then purified with a silica gel column, and methanolic ammonia (30 mL) was added thereto. The resulting mixture was stirred at room temperature for 24 hr. The reaction solution was concentrated and purified with a silica gel column and then with HPLC to yield 218 mg (54%, second stage yield) of 1-(2-deoxy-β-D-ribofuranosyl)-4-(N-dimethylaminosulfonyl-2-imidazolyl)-pyrrolo[2,3-b]pyridine. 1-(2-Deoxy-β-D-ribofuranosyl)-4-(N-dimethylaminosulfonyl-2-imidazolyl)-pyrrolo[2,3-b]pyridine (200 mg, 0.49 mmol) was dissolved in 80% acetic acid, followed by stirring at 60° C. for 3 hr. The reaction solution was concentrated, and aqueous ammonia was added thereto for further concentration. Subsequently, 1-(2-deoxy-β-D-ribofuranosyl)-4-(2-imidazolyl)-pyrrolo[2,3-b]pyridine (dDia: 109 mg, 74%) was obtained through purification by HPLC.

Workup

  1. concentrationThe reaction solution was concentrated
  2. customwas then purified with a silica gel column, and methanolic ammonia (30 mL)
  3. additionwas added
  4. stirringThe resulting mixture was stirred at room temperature for 24 hr
  5. concentrationThe reaction solution was concentrated
  6. custompurified with a silica gel column

Sources & evidence

ORD record
ord-916e9856ec514c9294b3aebad5e1da59
Source dataset
uspto-grants-2014_11
Patent number
US08895712B2

Reaction notes

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