Boron trifluoride etherate → HCID 67919650, compound

HRID 1196215Notes

Reaction equation

HRID 1196215 reaction equation
[BH4-].[Na+].B(F)(F)F.CC[O:9]CC.C=CCCC=CCC.[CH3:20][C:21]([C@H:23]1[N:26]([CH:27]([CH2:37][C:38]2[CH:43]=[CH:42][C:41]([O:44][CH3:45])=[CH:40][CH:39]=2)[CH2:28][C:29]2[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=2)[C:25](=[O:46])[C@@H:24]1[C@H:47]([O:49][C:50]([O:52][CH2:53][C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1)=[O:51])[CH3:48])=[CH2:22]>O1CCCC1>[OH:9][CH2:22][C@H:21]([C@H:23]1[N:26]([CH:27]([CH2:28][C:29]2[CH:30]=[CH:31][C:32]([O:35][CH3:36])=[CH:33][CH:34]=2)[CH2:37][C:38]2[CH:43]=[CH:42][C:41]([O:44][CH3:45])=[CH:40][CH:39]=2)[C:25](=[O:46])[C@@H:24]1[C@H:47]([O:49][C:50]([O:52][CH2:53][C:54]1[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=1)=[O:51])[CH3:48])[CH3:20]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 524697HCID 524697, compoundHCID 4311764Sodium borohydrideHCID 67796403HCID 67796403, compound

Product 1

HCID 67919650HCID 67919650, compoundYield 69.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of sodium borohydride (0.32 g) in dry tetrahydrofuran (40 ml) was added dropwise boron trifluoride-etherate (1.81 g) at 10°-20° C. under nitrogen gas, and the resultant mixture was stirred for 1 hour. After addition of 1,5-octadiene (1.21 g) and stirring for 1 hour, a solution of (3S,4S)-4-(1-methylethenyl)-3-(1-(R)-benzyloxycarbonyloxyethyl)-1-di(p-anisyl)methyl-2-azetidinone (2.63 g) in dry tetrahydrofuran (10 ml) was dropwise added thereto at 20°-25° C. over a period of 1 hour, followed by stirring for 3 hours. The reaction mixture was quenched with water (7 ml) at 10°-30° C. for 1 hour. After addition of 4% sodium bicarbonate solution (5.3 ml), the mixture was heated at 40°-45° C., treated with 35% hydrogen peroxide solution (5.3 ml) at 40°-45° C. and cooled down to room temperature. Sodium sulfite (0.2 g) and toluene (6 ml) were added to the mixture, followed by stirring. The organic layer was separated and the aqueous layer was extracted with toluene (12 ml). The combined extracts were washed with brine and dried over anhydrous sodium sulfate. Filtration and concentration of the filtrate in vacuo gave an oily residue, which was purified by silica gel chromatography to yield (3S,4R) 4-(1-(S)-hydroxymethylethyl)-3-(1-(R)-benzyloxycarbonyloxyethyl)-1-di(p-anisyl)methyl-2-azetidinone (1.88 g) and the corresponding 4-(1-(R)-hydroxymethylethyl) compound (0.51 g).

Workup

  1. waitat 20°-25° C. over a period of 1 hour
  2. stirringby stirring for 3 hours
  3. customThe reaction mixture was quenched with water (7 ml) at 10°-30° C. for 1 hour
  4. additionAfter addition of 4% sodium bicarbonate solution (5.3 ml)
  5. temperaturethe mixture was heated at 40°-45° C.
  6. additiontreated with 35% hydrogen peroxide solution (5.3 ml) at 40°-45° C.
  7. additionSodium sulfite (0.2 g) and toluene (6 ml) were added to the mixture
  8. stirringby stirring
  9. customThe organic layer was separated
  10. extractionthe aqueous layer was extracted with toluene (12 ml)
  11. washThe combined extracts were washed with brine
  12. dry with materialdried over anhydrous sodium sulfate
  13. filtrationFiltration and concentration of the filtrate in vacuo
  14. customgave an oily residue, which
  15. customwas purified by silica gel chromatography

Sources & evidence

ORD record
ord-2d92d00b2ef3468a8258fd4372f55b32
Source dataset
uspto-grants-1992_05
Patent number
US05112966

Reaction notes

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