Sodium borohydride → HCID 131734922, compound

HRID 921192Notes

Reaction equation

HRID 921192 reaction equation
[C:1]([O:5][C@@H:6]([C:12]1[C:13]([CH3:51])=[N:14][C:15]2[N:16]([N:29]=[C:30]([CH2:32][O:33][CH2:34][C:35]3[CH:40]=[CH:39][C:38]([F:41])=[CH:37][C:36]=3[O:42][CH:43]([CH2:48]C=C)[C:44]([F:47])([F:46])[F:45])[CH:31]=2)[C:17]=1[N:18]1[CH2:23][CH2:22][C:21]([CH3:28])([O:24][CH2:25][CH:26]=[CH2:27])[CH2:20][CH2:19]1)[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2].[BH4-].[Na+]>C(Cl)Cl.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1>[C:1]([O:5][C@@H:6]([C:12]1[C:13]([CH3:51])=[N:14][C:15]2=[CH:31][C:30]3=[N:29][N:16]2[C:17]=1[N:18]1[CH2:23][CH2:22][C:21]([CH3:28])([O:24][CH2:25][CH2:26][CH:27]=[CH:48][CH:43]([C:44]([F:46])([F:45])[F:47])[O:42][C:36]2[C:35]([CH2:34][O:33][CH2:32]3)=[CH:40][CH:39]=[C:38]([F:41])[CH:37]=2)[CH2:20][CH2:19]1)[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 118318852HCID 118318852, compound

Product 1

HCID 131734922HCID 131734922, compoundYield 70.4%

Reagents, catalysts & solvents 2

HCID 11147261(1,3-Dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichlorideCatalyst2×HCID 6344DichloromethaneSolvent

Procedure

Ethyl (2S)-2-(tert-butoxy)-2-{2-[({4-fluoro-2-[(1,1,1-trifluoropent-4-en-2-yl)oxy]phenyl}m ethoxy)methyl]-5-methyl-7-[4-methyl-4-(prop-2-en-1-yloxy)piperidin-1-yl]pyrazolo[1,5-a]pyrimidin-6-yl}acetate (90 mg, 0.125 mmol) was dissolved in 70 mL of CH2Cl2. To this was added [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (21 mg, 0.025 mmol) and the resulting mixture stirred at reflux for 4 hours. The solvent was removed under vacuum and the residue dissolved in 1 mL of methanol. [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (21 mg, 0.025 mmol) was added followed by NaBH4 (26 mg, 0.624 mmol). After stirring for 15 min the solvent was removed under vacuum and the crude product purified by chromatography on a Biotage instrument eluting with hexanes/ethyl acetate to provide 61 mg of product. LCMS (M+H)=695.5.

Workup

  1. temperatureat reflux for 4 hours
  2. customThe solvent was removed under vacuum
  3. dissolutionthe residue dissolved in 1 mL of methanol
  4. stirringAfter stirring for 15 min the solvent
  5. customwas removed under vacuum
  6. customthe crude product purified by chromatography on a Biotage instrument
  7. washeluting with hexanes/ethyl acetate

Sources & evidence

ORD record
ord-a00b819f382541c2a317dfa72a49fcee
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

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