m-Chloroperbenzoic acid → HCID 131735543, compound

HRID 522819Notes

Reaction equation

HRID 522819 reaction equation
[CH:1]([Si:4]1([CH:22]([CH3:24])[CH3:23])[O:11][C@H:10]2[C@@H:12]([OH:15])[CH:13]=[CH:14][C@@H:9]2[CH2:8][O:7][Si:6]([CH:19]([CH3:21])[CH3:20])([CH:16]([CH3:18])[CH3:17])[O:5]1)([CH3:3])[CH3:2].C1C=C(Cl)C=C(C(OO)=[O:33])C=1>ClCCl>[CH:22]([Si:4]1([CH:1]([CH3:3])[CH3:2])[O:11][C@H:10]2[CH:12]([OH:15])[C@@H:13]3[O:33][C@@H:14]3[C@@H:9]2[CH2:8][O:7][Si:6]([CH:16]([CH3:18])[CH3:17])([CH:19]([CH3:21])[CH3:20])[O:5]1)([CH3:24])[CH3:23]

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 131735542(+)-(6aR,9S,9aR)-2,2,4,4-Tetraisopropyl-6,6a,9,9a-tetrahydrocyclopenta[f][1,3,5,2,4]trioxad-isilocin-9-ol

Product 1

HCID 131735543HCID 131735543, compoundYield 85.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of compound 11 (13.7 g, 36.8 mmol) in dichloromethane (300 mL), m-CPBA (15.9 g, 92.0 mmol) was added portion wise at room temperature. The mixture was stirred at room temperature for 16 h, quenched with a saturated NaHCO3 solution and extracted with DCM (200 mL×2). The combined organic layer was washed with brine (100 mL×2) and dried over Na2SO4. The solvent was removed under reduced pressure and residue was purified by silica gel column chromatography (3% EtOAc/Hexane) to give epoxide 12 (12.2 g, 85%) as an oil. [α]24D +18.25° (c 1.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ 1.00-1.11 (m, 28H), 2.30 (in, 1H,), 3.05 (s, 1H), 3.37 (s, 1H), 3.56 (d, J=2.5 Hz, 1H), 3.99-4.05 (m, 2H), 4.19 (d, J=5.0 Hz, 1H), 4.26 (dd, J=3.0, 11.5 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 12.6, 13.1, 13.3, 17.0, 17.1, 17.2, 17.3, 17.4, 17.5, 48.2, 55.5, 58.4, 64.7, 70.7, 75.0; HR-MS Calcd. For (C18H36O5Si2+H)+ 389.2101. found 389.2171.

Workup

  1. customquenched with a saturated NaHCO3 solution
  2. extractionextracted with DCM (200 mL×2)
  3. washThe combined organic layer was washed with brine (100 mL×2)
  4. dry with materialdried over Na2SO4
  5. customThe solvent was removed under reduced pressure and residue
  6. customwas purified by silica gel column chromatography (3% EtOAc/Hexane)

Sources & evidence

ORD record
ord-2d00d929c19d43d7bf8f39051a93e3ae
Source dataset
uspto-grants-2016_05
Patent number
US09334273B1

Reaction notes

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