Sodium borohydride → HCID 66744447, compound

HRID 1959469Notes

Reaction equation

HRID 1959469 reaction equation
[C:1]([O:5][C:6]([N:8]([C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44])[C:9]1[C:10]([C:22]2[O:26][C:25]([C:27]3[CH:32]=[CH:31][C:30]([CH2:33][N:34]([CH3:42])[C:35](=[O:41])[O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[CH:29][CH:28]=3)=[N:24][N:23]=2)=[N:11][C:12]([C:15]2[CH2:20][CH2:19][C:18](=[O:21])[CH2:17][CH:16]=2)=[CH:13][N:14]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[BH4-].[Na+]>CO>[C:46]([O:45][C:43]([N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[C:9]1[C:10]([C:22]2[O:26][C:25]([C:27]3[CH:32]=[CH:31][C:30]([CH2:33][N:34]([CH3:42])[C:35](=[O:41])[O:36][C:37]([CH3:38])([CH3:39])[CH3:40])=[CH:29][CH:28]=3)=[N:24][N:23]=2)=[N:11][C:12]([C:15]2[CH2:20][CH2:19][CH:18]([OH:21])[CH2:17][CH:16]=2)=[CH:13][N:14]=1)=[O:44])([CH3:47])([CH3:48])[CH3:49]

Participants

4

Reactant 2

HCID 4311764Sodium borohydrideHCID 66745393HCID 66745393, compound

Product 1

HCID 66744447HCID 66744447, compoundYield 41%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of tert-butyl N-[[4-[5-[3-[bis(tert-butoxycarbonyl)amino]-6-(4-oxocyclohexen-1-yl)pyrazin-2-yl]-1,3,4-oxadiazol-2-yl]phenyl]methyl]-N-methyl-carbamate (431 mg, 0.64 mmol) in MeOH (2 mL) was cooled in an ice water bath. Sodium boranuide (27 mg, 0.70 mmol) was added and the reaction mixture was stirred for 40 minutes at 0° C. upon which the ice bath was removed. After stirring at room temperature for 8 h, the reaction mixture was quenched with water and aq. NaHCO3 and diluted with EtOAc. The layers were separated and the aqueous layer was extracted once more with EtOAc. The combined organic layer was dried over Na2SO4, filtered and concentrated. The crude material was purified by silica gel column chromatography using 0-40% EtOAc in DCM to yield tert-butyl N-[[4-[5-[3-[bis(tert-butoxycarbonyl)amino]-6-(4-hydroxycyclohexen-1-yl)pyrazin-2-yl]-1,3,4-oxadiazol-2-yl]phenyl]methyl]-N-methyl-carbamate (126 mg, 41%). 1H NMR (400 MHz, DMSO-d6) δ 9.04 (s, 1H), 8.11 (d, J=8.0 Hz, 2H), 7.49 (d, J=8.1 Hz, 2H), 7.01 (s, 1H), 4.81 (d, J=3.8 Hz, 1H), 4.49 (s, 2H), 3.93-3.86 (m, 1H), 2.83 (s, 5H), 2.64-2.53 (m, J=19.3 Hz, 2H), 1.97-1.90 (m, J=12.4 Hz, 1H), 1.71 (dd, J=14.0, 8.7 Hz, 1H), 1.45 (s, 3H), 1.36 (s, 6H), 1.26 (s, 18H); LC/MS m/z 579.9 [M+H]+.

Workup

  1. customwas removed
  2. customthe reaction mixture was quenched with water and aq. NaHCO3
  3. additiondiluted with EtOAc
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted once more with EtOAc
  6. dry with materialThe combined organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude material was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-e83b38076ce14999ba20a2b22b7a0caa
Source dataset
uspto-grants-2013_04
Patent number
US08410112B2

Reaction notes

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