Dimethyl methylphosphonate → HCID 14554062, compound

HRID 621758Notes

Reaction equation

HRID 621758 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[CH2:13]([O:20][C@@H:21]1[C@@H:27]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@H:26]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@@H:25]([CH2:44][O:45][CH2:46][C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)[O:24][C:22]1=[O:23])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>CCCCCC.O1CCCC1>[CH2:13]([O:20][C@@H:21]1[C@@H:27]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@H:26]([O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C@@H:25]([CH2:44][O:45][CH2:46][C:47]2[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=2)[O:24][C:22]1([OH:23])[CH2:6][P:7]([O:10][CH3:11])([O:8][CH3:9])=[O:12])[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

6

Reactant 3

HCID 12958Dimethyl methylphosphonateHCID 10907626(3R,4S,5R,6R)-3,4,5-Tris(benzyloxy)-6-((benzyloxy)methyl)oxan-2-oneHCID 178418339Butyllithium

Product 1

HCID 14554062HCID 14554062, compoundYield 90.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of n-butyllithium in n-hexane (1.6M solution, 68.8 ml) was added to a solution of dimethyl methylphosphonate (13.65 g) in tetrahydrofuran (200 ml) in a stream of argon at -70° to -78° C., and then stirred for 30 min. To the solution was added a solution of 2,3,4,6-tetra-O-benzyl-D-glucono-1,5-lactone (29.6 g) in tetrahydrofuran (150 ml) at -70° to -78° C. The mixture was stirred for 1 hour at the same temperature. The cooling bath was removed and the mixture was allowed to warm to 0° C. with stirring. Ice-cold 10% ammonium chloride solution (400 ml) was added to the reaction mixture and the resulting oily substances were extracted with ethyl acetate (1.2 l). The ethyl acetate solution was washed with 2N hydrochloric acid and saturated aqueous sodium hydrogen-carbonate, dried with anhydrous sodium sulfate and then evaporated in vacuo. Ethyl ether-petroleum ether (1:3; 400 ml) was added to the residue and the mixture was refrigerated to give 3,4,5,7-tetra-O-benzyl-1-deoxy-1-(dimethoxyphosphoryl)-D-gluco-2-heptulopyranose (33.1 g) as white crystals; m.p. 112°-113° C.;

Workup

  1. stirringThe mixture was stirred for 1 hour at the same temperature
  2. customThe cooling bath was removed
  3. stirringwith stirring
  4. additionIce-cold 10% ammonium chloride solution (400 ml) was added to the reaction mixture
  5. extractionthe resulting oily substances were extracted with ethyl acetate (1.2 l)
  6. washThe ethyl acetate solution was washed with 2N hydrochloric acid and saturated aqueous sodium hydrogen-carbonate
  7. dry with materialdried with anhydrous sodium sulfate
  8. customevaporated in vacuo
  9. additionEthyl ether-petroleum ether (1:3; 400 ml) was added to the residue

Sources & evidence

ORD record
ord-23d7f40009e74d92ae157e175f2ec13d
Source dataset
uspto-grants-1989_04
Patent number
US04824943

Reaction notes

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