Hydrogen Peroxide → HCID 102526945, compound

HRID 1056860Notes

Reaction equation

HRID 1056860 reaction equation
[Si:1]([O:8][C@H:9]([C@:11]1([NH:30][C:31]([N:33]([CH3:35])[CH3:34])=[O:32])[C@@H:15]([NH:16][C:17](=[O:26])[O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:14]=[C:13]([CH2:27][OH:28])[C:12]1=[O:29])[CH3:10])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C[OH:37].C(Cl)Cl.OO.[OH-].[Na+]>CCOCC>[Si:1]([O:8][C@H:9]([C@@:11]1([NH:30][C:31]([N:33]([CH3:35])[CH3:34])=[O:32])[C:12](=[O:29])[C@@:13]2([CH2:27][OH:28])[C@H:14]([O:37]2)[C@@H:15]1[NH:16][C:17](=[O:26])[O:18][CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[CH3:10])([C:4]([CH3:6])([CH3:5])[CH3:7])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 21226129Dichloromethane methanolHCID 102526940HCID 102526940, compound

Product 1

HCID 102526945HCID 102526945, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

A 200-mL round-bottomed flask was charged with enone 10 (1.1 g, 2.2 mmol, 1.0 equiv) and MeOH:CH2Cl2 (7:1, 32 mL). The resulting solution was cooled to 0° C., and a cooled solution of H2O2 (30% aq., 20 mL) and NaOH (20% aq., 5 mL) was added dropwise. The reaction was stirred at 0° C. for 2 h, and diluted with Et2O (30 mL). The layers were separated and the aqueous layer was extracted with Et2O (3×15 mL). The combined organics were washed with H2O (3×30 mL), brine (20 mL), dried with magnesium sulfate, and concentrated in vacuo. The crude product was purified via flash chromatography (70:30 petroleum ether:acetone) affording the title compound as a clear, viscous oil with >20:1 diastereoselection (0.91 g, 81%). Analytical data: [α]D19 −22.4 (c=1.00, CHCl3); 1H NMR (600 MHz, CDCl3): δ 7.32-7.26 (m, 5H), 5.66 (d, J=9.6 Hz, 1H), 5.20 (d, J=12.0 Hz, 1H), 4.93 (d, J=12.6 Hz, 1H), 4.68 (s, 1H), 4.68-4.66 (m, 1H), 4.07-4.04 (m, 2H), 4.02-3.98 (m, 2H), 2.64 (s, 6H), 1.15 (d, J=6.6 Hz, 3H), 0.89 (s, 9H), 0.11 (s, 3H), 0.10 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 204.4, 156.9, 156.0, 136.6, 128.3, 128.1, 128.0, 74.0, 69.3, 66.4, 65.9, 60.7, 56.0, 52.3, 36.1, 25.5, 18.2, 17.7, −3.9, −4.8; LRMS (ESI+) Calcd. for C25H39N3O7Si+, 522.26. Found, 522.23. IR (thin film, cm−1) 3402, 2954, 2857, 2359, 2249, 2125, 1650, 1519, 1227, 830, 732; TLC (70:30 petroleum ether/acetone): Rf=0.30.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer was extracted with Et2O (3×15 mL)
  3. washThe combined organics were washed with H2O (3×30 mL), brine (20 mL)
  4. dry with materialdried with magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe crude product was purified via flash chromatography (70:30 petroleum ether:acetone)

Sources & evidence

ORD record
ord-fe5075bc3f8e4aeda9af9b3a9494d2ca
Source dataset
uspto-grants-2016_07
Patent number
US09399652B2

Reaction notes

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