Hydrogen Peroxide → HCID 11171416, compound

HRID 842434Notes

Reaction equation

HRID 842434 reaction equation
[CH3:1][C@@H:2]1[CH2:7][CH2:6][C:5](=[O:8])[CH2:4][C@H:3]1[C:9]([O:11][CH2:12][CH3:13])=[O:10].CCC(C)[BH-](C(C)CC)C(C)CC.[K+].OO>C1COCC1>[OH:8][C@@H:5]1[CH2:4][C@@H:3]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C@H:2]([CH3:1])[CH2:7][CH2:6]1

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 4304157Potassium;tri(butan-2-yl)boranuideHCID 11206192HCID 11206192, compound

Product 1

HCID 11171416HCID 11171416, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-50 °C

Procedure

To a cold (−78° C.) solution of 11 (14.9 g, 80.8 mmol) in THF (250 mL) was added K-Selectride (potassium tri-sec-butylborohydride) (95.0 mmol, 1.0 M in THF). After addition was complete, the mixture was allowed to warm to −50° C. and stirred for an additional 4 h, whereupon the reaction was complete by TLC. The reaction was quenched by addition to 2.2 M NaH2PO4/K2HPO4 buffer (300 mL, pH =7). This was cooled (0° C.) and 30% hydrogen peroxide (42 mL, 370 mmol) was added and the mixture was allowed to stir overnight. The layers were separated and the aqueous layer was extracted with ethyl acetate (4×200 mL). The combined organics were washed with brine (300 mL), 1.0 M sodium sulfite (300 mL), dried (MgSO4) and the volatiles were removed in vacuo to yield an oil which was further purified by flash chromatography (12.48 g, 83% yield). Rf 0.35 (ethyl acetate/hexane 3:7); 1H NMR (300 MHz, CDCl3) δ 4.45-4.54 (m, 1H), 4.10 (q, J=7.2, 2H), 2.34-2.44 (m, 1H), 2.00-2.30 (b, 1H), 1.26-1.91 (m, 7H), 1.22 (t, J=7.2, 3H), 0.89 (d, J=6.4, 3H); 13C NMR (75 MHz, CDCl3) δ 176.1, 65.4, 60.0, 45.1, 35.8, 33.9, 32.0, 27.6, 20.2, 14.2; MS (EI) m/z 186 (M+, 3), 168 ([M-H2O]+, 37), 141 ([M-OCH2CH3]+, 25), 130 (12), 95 (100), 73 (27), 55 (34); [α]D−27.4° (c=1.10, CH2Cl2). Analysis calcs'd for C10H18O3: C, 64.49; H, 9.74. Found: C, 64.19; H, 9.62.

Workup

  1. additionAfter addition
  2. customThe reaction was quenched by addition to 2.2 M NaH2PO4/K2HPO4 buffer (300 mL, pH =7)
  3. additionwas added
  4. stirringto stir overnight
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate (4×200 mL)
  7. washThe combined organics were washed with brine (300 mL), 1.0 M sodium sulfite (300 mL)
  8. dry with materialdried (MgSO4)
  9. customthe volatiles were removed in vacuo
  10. customto yield an oil which
  11. customwas further purified by flash chromatography (12.48 g, 83% yield)

Sources & evidence

ORD record
ord-30b4c768a91c4594839938b1566c933f
Source dataset
uspto-grants-2002_04
Patent number
US06375943B1

Reaction notes

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