Hydrogen Peroxide → HCID 57125386, compound

HRID 2260480Notes

Reaction equation

HRID 2260480 reaction equation
[C:1]([C@:9]1([N+:22]([O-:24])=[O:23])[C@H:14]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C@@H:13]2[CH2:21][C@H:10]1[CH:11]=[CH:12]2)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B1C2CCCC1CCC2.[OH-:34].[Na+].OO>C1COCC1.CCO>[C:1]([C@@:9]1([N+:22]([O-:24])=[O:23])[C@H:10]2[CH2:21][C@H:13]([CH2:12][C@@H:11]2[OH:34])[C@H:14]1[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 86749167HCID 86749167, compound

Product 1

HCID 57125386HCID 57125386, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
25 °C

Procedure

A solution of Compound 9 (2.20 g, 6.90 mmol) in THF (18 mL, 0.38M) was treated with 9-BBN (8.62 mmol, 1.25 equiv) in THF (17.25 mL, 0.5M) and the mixture was allowed to stir at 25° C. under N2 for 10 hours. The resulting mixture was treated successively with 4.15 mL of EtOH, 1.5 mL of 20 percent aqueous NaOH, and 1.65 mL of 50 percent aqueous H2O2. The reaction solution was warmed at 50° C. for one hour, recooled to 25° C., and partitioned between EtOAc (200 mL) and H2O (200 mL). The EtOAc layer was dried (Na2SO4) and concentrated under reduced pressure. Chromatography (SiO2, 5×15 cm, 10-25 percent EtOAc-hexane gradient elution) afforded the major isomer Compound 10 (1.29 g, 55.5 percent; Rf =0.32, 20 percent EtOAc-hexane) and Compound 11 (1S*,2R*,4S*,5R*,6S*-5-benzoyl-2-hydroxy-5-nitro-6-phenyl-bicyclo[[2.2.1]heptane, 400 mg, 17.2 percent; Rf =0.26, 20 percent EtOAc-hexane) as white solids cleanly separated from one another in a 3.2:1 ratio (1.69 g total, 2.32 g theoretical, 73 percent). For Compound 10: mp 168°-169° C. (EtOAc-hexane, colorless needles); 1H NMR (CDCl3, 250 MHz) δ7.38 (d, 2H, J=8.2 Hz), 7.31-6.94 (m, 8H), 4.33 (d, 1H, J=2.4 Hz, C5-H), 3.85 (d, 1H, J=6.8, C2-H), 3.29 (s, 1H, C1-H), 2.63 (d, J=11.3 Hz, C7-H syn to ketone), 2.46 (d, 1H, J=4.3 Hz, C4-H), 2.26-2.16 (m, 2H), 1.67-1.60 (m, 2H); 13C NMR (CDCl3, 50 MHz) δ189.9, 138.8, 133.7, 133.0, 128.9, 128.5, 128.3, 127.8, 127.4, 105.0, 69.3, 55.5, 55.4, 44.6, 42.1, 35.7; IR (neat) vmax 3331, 2968, 2900, 1689, 1538, 1444, 1353, 1234, 1096, 1063 cm-1 ; FABHRMS (NBA-NaI) m/e 360.1230 (C20H19NO4+Na+ requires 360.1212). Anal. Calcd for C20H19NO4 : C, 71.20; H, 5.68; N, 4.15. Found: C, 71.13; H, 5.89; N, 4.10. For Compound 11: 1H NMR (CDCl3, 250 MHz) δ7.34 (d, 2H, J=8.0 Hz), 7.25-6.90 (m, 8H), 4.18 (m, 2H), 3.25 (m, 1H), 2.62 (d, 1H, J=11.2 Hz), 2.26 (s, 1H), 2.12 (d, 1H, J=11.4 Hz), 1.80-1.62 (m, 2H), 1.45 (m, 1H); FABHRMS (NBA-CsI) m/e 470.0368 (C2H19NO4 +Cs+ requires 470.0368).

Workup

  1. temperatureThe reaction solution was warmed at 50° C. for one hour
  2. customrecooled to 25° C.
  3. custompartitioned between EtOAc (200 mL) and H2O (200 mL)
  4. dry with materialThe EtOAc layer was dried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. washChromatography (SiO2, 5×15 cm, 10-25 percent EtOAc-hexane gradient elution)

Sources & evidence

ORD record
ord-788c72db15e94294b921aede6c90812f
Source dataset
uspto-grants-1995_12
Patent number
US05478728

Reaction notes

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