Ethanol → 4-Tert-butyl-2-cyclopentenyl-5-nitrophenyl methyl carbonate

HRID 471917Notes

Reaction equation

HRID 471917 reaction equation
[C:1](=[O:19])([O:17][CH3:18])[O:2][C:3]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:6]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:5][C:4]=1Br.[C:20]1(B(O)O)[CH2:24][CH2:23][CH2:22][CH:21]=1.C([O-])([O-])=O.[Na+].[Na+].C(O)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[C:1](=[O:19])([O:17][CH3:18])[O:2][C:3]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:6]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:5][C:4]=1[C:20]1[CH2:24][CH2:23][CH2:22][CH:21]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 3861343(Cyclopent-1-en-1-yl)boronic acidHCID 593950502-Bromo-4-tert-butyl-5-nitrophenyl methyl carbonate

Product 1

HCID 593950444-Tert-butyl-2-cyclopentenyl-5-nitrophenyl methyl carbonateYield 40%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A microwave tube was charged with 2-bromo-4-tert-butyl-5-nitrophenyl methyl carbonate (200 mg, 0.60 mmol), 1-cyclopentenylboronic acid (91 mg, 0.81 mmol), Pd(PPh3)4 (69 mg, 0.06 mmol), 2 M Na2CO3 (1.5 mL), ethanol (1.5 mL) and toluene (3 mL) under inert atmosphere and was heated under microwave irradiation at 80° C. for 4 h. The reaction was extracted with ethyl acetate then washed with saturated NaHCO3 and brine. The organic layer was dried over Na2SO4, filtered and concentrated. Purification by silica gel chromatography (0-30% ethyl acetate/hexanes) provided 4-tert-butyl-2-cyclopentenyl-5-nitrophenyl methyl carbonate (76 mg, 40% yield). 1H NMR (400.0 MHz, DMSO-d6) δ 7.69 (s, 1H), 7.57 (s, 1H), 6.28 (t, J=1.9 Hz, 1H), 3.86 (d, J=12.5 Hz, 3H), 2.69 (td, J=7.5, 3.2 Hz, 2H), 1.93 (dd, J=7.6, 15.0 Hz, 2H), 1.36-1.33 (m, 11H).

Workup

  1. extractionThe reaction was extracted with ethyl acetate
  2. washthen washed with saturated NaHCO3 and brine
  3. dry with materialThe organic layer was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by silica gel chromatography (0-30% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-3cf2e07972cc4c1ab67c0adc607f9cd1
Source dataset
uspto-grants-2014_01
Patent number
US08633189B2

Reaction notes

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