Boron Trichloride → (2R,3R,4R,5R)-2-(2-amino-4-chloropyrrolo[2,3-d]pyrimidin-7-yl)-5-(hydroxymethyl)-3-methyloxolane-3,4-diol

HRID 448687Notes

Reaction equation

HRID 448687 reaction equation
[NH2:1][C:2]1[N:3]=[C:4]([Cl:39])[C:5]2[CH:10]=[CH:9][N:8]([C@@H:11]3[O:26][C@H:25]([CH2:27][O:28]CC4C=CC(Cl)=CC=4Cl)[C@@H:14]([O:15]CC4C=CC(Cl)=CC=4Cl)[C@@:12]3([CH3:38])[OH:13])[C:6]=2[N:7]=1.B(Cl)(Cl)Cl>C(Cl)Cl>[NH2:1][C:2]1[N:3]=[C:4]([Cl:39])[C:5]2[CH:10]=[CH:9][N:8]([C@@H:11]3[O:26][C@H:25]([CH2:27][OH:28])[C@@H:14]([OH:15])[C@@:12]3([CH3:38])[OH:13])[C:6]=2[N:7]=1

Participants

4

Reactant 2

HCID 25135Boron TrichlorideHCID 112390772-Amino-4-chloro-7-[3,5-bis-O-(2,4-dichlorophenylmethyl)-2-C-methyl-beta-D-ribofuranosyl)-7H-pyrrolo[2,3-d]pyrimidine

Product 1

HCID 11483860(2R,3R,4R,5R)-2-(2-amino-4-chloropyrrolo[2,3-d]pyrimidin-7-yl)-5-(hydroxymethyl)-3-methyloxolane-3,4-diolYield 79.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of the product from Step A (630 mg, 1.0 mmol) in CH2Cl2 (20 mL) at −78° C. was added boron trichloride (1M in CH2Cl2) (10 mL, 10 mmol). The mixture was stirred at −78° C. for 2 h, then at −20° C. for 2.5 h. The reaction was quenched with CH2Cl2/MeOH (1:1) (10 mL), stirred at −20° C. for 0.5 h, and neutralized at 0° C. with aqueous ammonia. The solid was filtered, washed with CH2Cl2/MeOH (1:1) and the combined filtrate evaporated in vacuo. The residue was purified on a silica gel column with CH2Cl2/MeOH, 50/1 and 20/1 as eluent to give the title compound as a colorless foam (250 mg).

Workup

  1. waitat −20° C. for 2.5 h
  2. customThe reaction was quenched with CH2Cl2/MeOH (1:1) (10 mL)
  3. stirringstirred at −20° C. for 0.5 h
  4. customneutralized at 0° C. with aqueous ammonia
  5. filtrationThe solid was filtered
  6. washwashed with CH2Cl2/MeOH (1:1)
  7. customthe combined filtrate evaporated in vacuo
  8. customThe residue was purified on a silica gel column with CH2Cl2/MeOH, 50/1 and 20/1 as eluent

Sources & evidence

ORD record
ord-fa3ee95cfef74924b60fffe0115dadc0
Source dataset
uspto-grants-2013_07
Patent number
US08481712B2

Reaction notes

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