Carbon tetrabromide → HCID 67430334, compound

HRID 1660720Notes

Reaction equation

HRID 1660720 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH:12]2[CH2:13][CH2:14][CH:9]1[C:10]([C:15]1[C:16]([CH2:23][CH2:24]O)=[CH:17][C:18]([O:21][CH3:22])=[N:19][CH:20]=1)=[CH:11]2)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(Br)(Br)(Br)[Br:27].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH:12]2[CH2:13][CH2:14][CH:9]1[C:10]([C:15]1[C:16]([CH2:23][CH2:24][Br:27])=[CH:17][C:18]([O:21][CH3:22])=[N:19][CH:20]=1)=[CH:11]2)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 67430679HCID 67430679, compound

Product 1

HCID 67430334HCID 67430334, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 7-tert-butoxycarbonyl-2-[4-(2-hydroxyethyl)-2-methoxy-5-pyridinyl]-7-azabicyclo[2.2.1]hept-2-ene (390 mg, 1.13 mmol) in dry CH2Cl2 (20 mL) under N2 was added CBr4 (745 mg, 2.25 mmol). The mixture was stirred at room temperature for 10 min, and then a solution of PPh3 (590 mg, 2.25 mmol) in dry CH2Cl2 (5 mL) was slowly added. After that the reaction mixture was stirred at room temperature for 2 h and quenched by water, and then diluted with CH2Cl2. The organic layer was separated and washed with brine, dried (Na2SO4), and concentrated. The residue was purified by chromatography with hexane/EtOAc (6:1) to afford 7-tert-butoxycarbonyl-2-[4-(2-bromoethyl)-2-methoxy-5-pyridinyl]-7-azabicyclo[2.2.1]hept-2-ene as a syrup (400 mg, 87%). 1H NMR (CDCl3) δ 7.95 (br s, 1H), 6.66 (s, 1H), 6.23 (br s, 1H), 4.86 (d, 1H, J=3.6 Hz), 4.81 (br s, 1H), 3.94 (s, 3H), 3.59-3.46 (m, 2H), 3.42-3.12 (m, 2H), 2.09-1.92 (m, 2H), 1.45 (s, 9H), 1.36-1.20 (m, 2H); 13C NMR (CDCl3) δ 163.83, 155.35, 148.55, 146.16, 144.63, 132.04, 123.16, 111.15, 80.16, 63.16, 61.35, 53.44, 35.97, 30.76, 28.20, 25.96 and 25.32, 24.55 and 23.62.

Workup

  1. stirringAfter that the reaction mixture was stirred at room temperature for 2 h
  2. customquenched by water
  3. additiondiluted with CH2Cl2
  4. customThe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. customThe residue was purified by chromatography with hexane/EtOAc (6:1)

Sources & evidence

ORD record
ord-1b612aef2e894565898467e1b5652e0b
Source dataset
uspto-grants-2011_10
Patent number
US08030300B2

Reaction notes

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