Hydrogen Peroxide → HCID 25140027, compound

HRID 1669110Notes

Reaction equation

HRID 1669110 reaction equation
B1C2CCCC1CCC2.[CH2:10]([C:13]1[N:14]=[N+:15]([O-:35])[C:16]2[CH:25]=[C:24]3[C:20]([CH2:21][CH:22]([CH2:26][O:27][Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])[CH2:23]3)=[CH:19][C:17]=2[N:18]=1)[CH:11]=[CH2:12].C([O-])(=[O:38])C.[Na+].OO>C1COCC1.CO>[Si:28]([O:27][CH2:26][CH:22]1[CH2:21][C:20]2[C:24](=[CH:25][C:16]3[N+:15]([O-:35])=[N:14][C:13]([CH2:10][CH2:11][CH2:12][OH:38])=[N:18][C:17]=3[CH:19]=2)[CH2:23]1)([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:29])[CH3:30]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 517045Sodium AcetateHCID 25139189HCID 25139189, compound

Product 1

HCID 25140027HCID 25140027, compoundYield 49.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
20 °C

Procedure

A solution of 9-BBN (0.5 M, 32.5 mL, 16.3 mmol) in THF was added to a stirred solution of alkene 137 (4.02 g, 10.8 mmol) in THF (50 mL) at 20° C. under N2 and the mixture was stirred at 20° C. for 30 min. The mixture was cooled to 0° C., a solution of sodium acetate (3 M, 25 mL, 75 mmol) and then H2O2 (70%, 25 mL, 468 mmol) were added carefully and stirred for 10 min. MeOH (100 mL) was added and the mixture stirred at 20° C. for 20 min. The mixture was partitioned between aqueous Na2CO3 solution and EtOAc. The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, using a gradient (50-70%) of EtOAc/pet. ether, to give alcohol 138 (2.08 g, 49%) as a pale yellow solid: mp (EtOAc/pet. ether) 93-94° C.; 1H NMR δ 8.22 (s, 1H, H-9), 7.72 (s, 1H, H-5), 3.79 (br q, J=5.1 Hz, 2H, CH2O), 3.59-3.67 (m, 2H, CH2OSi), 3.12-3.24 (m, 4H, CH2), 2.93-3.03 (m, 2H, CH2), 2.73-2.84 (m, 1H, H-7), 2.30 (br s, 1H, OH), 2.11-2.21 (m, 2H, CH2), 0.87 [s, 9H, SiC(CH3)3], 0.04 [s, 6H, Si(CH3)2]; 13C NMR δ 165.7, 154.2, 148.3, 147.3, 132.3, 122.8, 114.5, 65.4, 62.2, 42.0, 35.8, 35.5, 34.0, 30.6, 25.8 (3), 18.3, −5.41 (2). Anal. calcd for C20H31N3O3S.¼H2O: C, 61.7; H, 8.0; N, 10.8. Found: C, 61.5; H, 7.8; N, 10.9%.

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. stirringstirred for 10 min
  3. stirringthe mixture stirred at 20° C. for 20 min
  4. customThe mixture was partitioned between aqueous Na2CO3 solution and EtOAc
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography

Sources & evidence

ORD record
ord-f3abd591b8cb47418124e9fb8a96ecea
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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