Sodium borohydride → HCID 118318885, compound

HRID 921241Notes

Reaction equation

HRID 921241 reaction equation
[CH2:1]([C:4]1[CH:44]=[C:43]([F:45])[CH:42]=[CH:41][C:5]=1[CH2:6][O:7][CH2:8][C:9]1[CH:40]=[C:12]2[N:13]=[C:14]([CH3:39])[C:15]([C@H:28]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])[C:29]([O:31][CH2:32][CH3:33])=[O:30])=[C:16]([N:17]3[CH2:22][CH2:21][C:20]([O:24][CH2:25][CH:26]=[CH2:27])([CH3:23])[CH2:19][CH2:18]3)[N:11]2[N:10]=1)C=C.[BH4-].[Na+]>Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1.C(Cl)Cl>[C:35]([O:34][C@@H:28]([C:15]1[C:14]([CH3:39])=[N:13][C:12]2=[CH:40][C:9]3=[N:10][N:11]2[C:16]=1[N:17]1[CH2:22][CH2:21][C:20]([CH3:23])([O:24][CH2:25][CH2:26][CH2:27][CH2:1][C:4]2[CH:44]=[C:43]([F:45])[CH:42]=[CH:41][C:5]=2[CH2:6][O:7][CH2:8]3)[CH2:19][CH2:18]1)[C:29]([O:31][CH2:32][CH3:33])=[O:30])([CH3:37])([CH3:38])[CH3:36]

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 118318883HCID 118318883, compound

Product 1

HCID 118318885HCID 118318885, compoundYield 44.7%

Reagents, catalysts & solvents 2

HCID 178425456HCID 178425456, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of (S)-ethyl 2-(2-(((2-allyl-4-fluorobenzyl)oxy)methyl)-7-(4-(allyloxy)-4-methylpiperidin-1-yl)-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-(tert-butoxy)acetate (70 mg, 0.112 mmol) and Grubbs II catalyst (95 mg, 0.112 mmol) in DCM (70 mL) was refluxed for 2 h. It was then concentrated and the residue was dissolved in MeOH (2 mL). Sodium borohydride (4.25 mg, 0.112 mmol) was added and the reaction mixture was stirred at rt for 1 h. It was then extracted with EtOAc, washed with water. The organic layer was dried over MgSO4, filtered and concentrated. The residue was purified by biotage, eluting with 20% EtOac/hexane to isolate ethyl (2S)-2-(tert-butoxy)-2-{16-fluoro-4,24-dimethyl-11,23-dioxa-1,5,7,8-tetraazapentacyclo[22.2.2.16,9.02,7.013,18]nonacosa-2,4,6(29),8,13(18),14,16-heptaen-3-yl}acetate (30 mg, 0.050 mmol, 44.7% yield) as a white solid. LCMS (M+1)=597.3.

Workup

  1. temperaturewas refluxed for 2 h
  2. concentrationIt was then concentrated
  3. dissolutionthe residue was dissolved in MeOH (2 mL)
  4. extractionIt was then extracted with EtOAc
  5. washwashed with water
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by biotage
  10. washeluting with 20% EtOac/hexane

Sources & evidence

ORD record
ord-c944a06a4f8b4e0eb2b226a8457240d5
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

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