Acetone → 4-(2-Hexanon-1-yl)-1-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)-pyrimidin-2-one

HRID 840609Notes

Reaction equation

HRID 840609 reaction equation
[C:1]([C:7]1[CH:12]=[CH:11][N:10]([C@@H:13]2[O:35][C@H:34]([CH2:36][O:37][C:38](=[O:45])[C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[C@@H:24]([O:25][C:26](=[O:33])[C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C@H:14]2[O:15][C:16](=[O:23])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:9](=[O:46])[N:8]=1)#[C:2][CH2:3][CH2:4][CH2:5][CH3:6].CC(C)=[O:49]>CC(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O.O.ClCCl.[Hg](OC(C)=O)OC(C)=O>[CH2:1]([C:7]1[CH:12]=[CH:11][N:10]([C@@H:13]2[O:35][C@H:34]([CH2:36][O:37][C:38](=[O:45])[C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[C@@H:24]([O:25][C:26](=[O:33])[C:27]3[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=3)[C@H:14]2[O:15][C:16](=[O:23])[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:9](=[O:46])[N:8]=1)[C:2](=[O:49])[CH2:3][CH2:4][CH2:5][CH3:6]

Participants

6

Reactant 2

HCID 180AcetoneHCID 103941024-(1-Hexyn-1-yl)-1-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)-pyrimidin-2-one

Product 1

HCID 867554054-(2-Hexanon-1-yl)-1-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)-pyrimidin-2-one

Reagents, catalysts & solvents 3

HCID 16683746DiacetyloxymercuryCatalystHCID 6344DichloromethaneSolventHCID 131721792acetic H2OSolvent

Procedure

A solution of 14a (0.77 g, 1.2 mmol) in 50 mL acetone is treated with a 0.1 M solution of Hg(OAc)2 (15 mL) in aqueous acetic-H2O (1:1) and the mixture stirred at room temperature for 18 hr. The reaction is further diluted with dichloromethane (100 mL), washed with cold saturated NaHCO3 solution, dried over magnesium sulfate and evaporated in vacuo. The resulting residue is flash-chromatographed using chloroform/acetone 19:1 to afford a yellowish solid. This solid is triturated with cold methanol to afford 15a, 0.47 g, 59%. 1H-NMR (DMSO-d6): 12.5 (s, 1H, enol); 8.0-7.4 (m, 16H, H-6 plus aromatic 6.15 (d, 1H, H-1′, J=2 Hz); 5.90 (m, 3H, H-5,2′,3′; 5.39 (s, 1H, vinylic, Jvinyl, allyl=<1 Hz)); 2.30, 1.47, 1.24 and 0.86 (4 m, 9H, n-butyl). Anal. Calcd for C36H34N2O8: C, 67.70; H, 5.37; N, 4.39. Found: C, 67.51; H, 5.28; N, 4.28.

Workup

  1. washwashed with cold saturated NaHCO3 solution
  2. dry with materialdried over magnesium sulfate
  3. customevaporated in vacuo
  4. customThe resulting residue is flash-chromatographed
  5. customto afford a yellowish solid
  6. customThis solid is triturated with cold methanol

Sources & evidence

ORD record
ord-34680d607d1c47b3a3f1f6cb00763423
Source dataset
uspto-grants-2002_04
Patent number
US06369040B1

Reaction notes

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