Ethyl acetate hexane → HCID 57911445, compound

HRID 1099172Notes

Reaction equation

HRID 1099172 reaction equation
CS(O[C@@H:6]1[C:16]2[C:11](=[N:12][CH:13]=[CH:14][CH:15]=2)[C@H:10]([O:17][Si:18]([CH:25]([CH3:27])[CH3:26])([CH:22]([CH3:24])[CH3:23])[CH:19]([CH3:21])[CH3:20])[CH2:9][CH2:8][C@H:7]1[C:28]1[CH:33]=[CH:32][CH:31]=[C:30]([F:34])[C:29]=1[F:35])(=O)=O.[Li+].[B-](CC)(CC)CC.CCOC(C)=O.CCCCCC>C1COCC1>[F:35][C:29]1[C:30]([F:34])=[CH:31][CH:32]=[CH:33][C:28]=1[C@@H:7]1[CH2:8][CH2:9][C@@H:10]([O:17][Si:18]([CH:22]([CH3:24])[CH3:23])([CH:25]([CH3:27])[CH3:26])[CH:19]([CH3:20])[CH3:21])[C:11]2=[N:12][CH:13]=[CH:14][CH:15]=[C:16]2[CH2:6]1

Participants

5

Reactant 3

HCID 21226206Ethyl acetate hexaneHCID 23712863Lithium triethylborohydrideHCID 57911464HCID 57911464, compound

Product 1

HCID 57911445HCID 57911445, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In a 21 flask was (5S,6S,9R)-6-(2,3-difluorophenyl)-9-(triisopropylsilyloxy)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-yl methanesulfonate (55.2 g, 105 mmol) (azeotroped with dry benzene) in THF (300 mL) to give a tan solution. Superhydride (525 mL, 525 mmol) (1.0M in THF) was added dropwise via dropping funnel under nitrogen, and the mixture was stirred at rt for 4 h. THF was stripped off and the tan oil was partitioned between water (300 ml) and EtOAc (400 ml). The layers were separated and the organic layer was washed with brine, dried and concentrated to a tan oil (close to 60 g). Purification by FCC (2.5 L packed column) up to 30% EtOAc/hexane did not give good purification but did get rid of baseline (not very uv active) junk (use just a silica plug and <10% EtOAc/hexane should be ok too). All the collected less polar fractions were combined and concentrated to a tan oil (33.58 g) and was directly used in the next step. MS (ESI)[M+H+]=432.19.

Workup

  1. customto give a tan solution
  2. customthe tan oil was partitioned between water (300 ml) and EtOAc (400 ml)
  3. customThe layers were separated
  4. washthe organic layer was washed with brine
  5. customdried
  6. concentrationconcentrated to a tan oil (close to 60 g)
  7. customPurification by FCC (2.5 L packed column) up to 30% EtOAc/hexane
  8. customdid not give good
  9. custompurification
  10. customdid get
  11. customAll the collected less polar fractions
  12. concentrationconcentrated to a tan oil (33.58 g)

Sources & evidence

ORD record
ord-47b2aaeab1784a15b5aa7a093f4df8d9
Source dataset
uspto-grants-2012_03
Patent number
US08143403B2

Reaction notes

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