Hydrogen Peroxide → HCID 57751174, compound

HRID 335678Notes

Reaction equation

HRID 335678 reaction equation
[CH2:1]([O:8][C:9]([NH:11][N:12]([C@H:23]([C:27]([CH3:30])([CH3:29])[CH3:28])[CH2:24][CH:25]=[CH2:26])[C:13](=[O:22])[C:14]1[CH:19]=[C:18]([CH3:20])[CH:17]=[C:16]([CH3:21])[CH:15]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CSC.B.[OH:35]O.[OH-].[Na+]>C1COCC1.O>[CH2:1]([O:8][C:9]([NH:11][N:12]([C@H:23]([C:27]([CH3:30])([CH3:29])[CH3:28])[CH2:24][CH2:25][CH2:26][OH:35])[C:13](=[O:22])[C:14]1[CH:15]=[C:16]([CH3:21])[CH:17]=[C:18]([CH3:20])[CH:19]=1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 12423031(Dimethyl sulfide)trihydroboronHCID 57751178HCID 57751178, compound

Product 1

HCID 57751174HCID 57751174, compoundYield 61.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (S)—N′-(1-tert-butyl-but-3-enyl)-N′-(3,5-dimethyl-benzoyl)-hydrazinecarboxylic acid benzyl ester (200 mg, 0.49 mmol) in THF (3 mL), was added borane dimethyl sulfide (2 M in THF, 125 μL, 0.25 mmol) at 0° C. The mixture was stirred at room temperature for 16 h. Excess borane and THF was removed in vacuo, and additional THF (3 mL), followed by H2O2 (61 microliters, 0.54 mmol) and 3N NaOH (90 microliters, 0.27 mmol) were added. After stirring at 50-55° C. for 1 h, more water was added, the mixture was extracted with ether, and the ether layer was dried over anhydrous Na2SO4. The solvent was removed in vacuo and the residue was purified by flash chromatography to give (S)—N′-(1-tert-butyl-4-hydroxy-butyl)-N′-(3,5-dimethyl-benzoyl)-hydrazinecarboxylic acid benzyl ester as a white solid (128 mg, yield 61%). Rf=0.30 (1:1 EtOAc:n-hexane). 1H NMR (400 MHz, DMSO-d6) δ 9.71+9.63 (2s, 1H), 7.44-6.88 (m, 8H), 5.06 (dd, J=3.6, 12.8 Hz, 1H), 4.79 (dd, J=12.4, 25.2 Hz, 1H), 4.43 (d, J=10.8 Hz, 1H), 4.28 (t, J=5.2 Hz, 1H), 3.47 (m, 2H), 2.27 (s, 6H), 1.86-1.21 (m, 4H), 1.01 (s, 9H); HRMS (ESI) m/z calcd for C25H35N2O4 [M+H]+ 427.2597. found 427.2587, calcd for C25H34N2NaO4 [M+Na]+ 449.2416. found 449.2407.

Workup

  1. customExcess borane and THF was removed in vacuo, and additional THF (3 mL)
  2. additionwere added
  3. stirringAfter stirring at 50-55° C. for 1 h
  4. extractionthe mixture was extracted with ether
  5. dry with materialthe ether layer was dried over anhydrous Na2SO4
  6. customThe solvent was removed in vacuo
  7. customthe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-08e9525a50d24eb697662505ef7a806a
Source dataset
uspto-grants-2014_11
Patent number
US08884060B2

Reaction notes

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