Dichloromethane → HCID 59854593, compound

HRID 2375916Notes

Reaction equation

HRID 2375916 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[F:11].C(=O)([O-])[O-].[K+].[K+].[C:18]([O:22][C:23]([N:25]1[CH2:30][CH:29]=[C:28](B2OC(C)(C)C(C)(C)O2)[CH2:27][CH2:26]1)=[O:24])([CH3:21])([CH3:20])[CH3:19].C(Cl)Cl>O1CCOCC1.O>[C:18]([O:22][C:23]([N:25]1[CH2:26][CH:27]=[C:28]([C:2]2[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=2[F:11])[CH2:29][CH2:30]1)=[O:24])([CH3:21])([CH3:19])[CH3:20]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 696992-Bromo-1-fluoro-4-nitrobenzeneHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 59854593HCID 59854593, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Into a 1-neck round-bottom flask were added 2-bromo-1-fluoro-4-nitrobenzene (1760 mg, 8.000 mmol), potassium carbonate (2210 mg, 16.00 mmol), 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (2720 mg, 8.800 mmol), water (8 mL) and 1,4-dioxane (32 mL). The flask was degassed and filled with N2 for 3 times, and then [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) complex with CH2Cl2 (1:1) (330.0 mg, 0.4000 mmol) was added. The mixture was degassed and filled with N2 for 3 times again and was then heated at 100° C. for 16 h. After that time, the mixture was concentrated in vacuo and was then purified by silica gel (240 g) eluting with 1800 mL of 5%, 1000 mL of 10%, 1000 mL of 15% and 1000 mL of 20% EtOAc/hexane to obtain the title compound as a colorless oil. 1H NMR (DMSO-d6, 400 MHz): δ=1.49 (s, 9H), 2.52-2.55 (m, 2H), 3.60 (t, 2H, J=5.6 Hz), 4.09 (brs, 2H), 6.21 (brs, 1H), 7.55-7.60 (m, 1H), 8.21-8.29 (m, 2H). MS (ES+): m/z 223.22 (100) [MH+-Boc]. HPLC: tR=3.83 min (ZQ2000, polar—5 min).

Workup

  1. customThe flask was degassed
  2. additionfilled with N2 for 3 times
  3. customThe mixture was degassed
  4. additionfilled with N2 for 3 times again
  5. concentrationAfter that time, the mixture was concentrated in vacuo
  6. customwas then purified by silica gel (240 g)
  7. washeluting with 1800 mL of 5%, 1000 mL of 10%, 1000 mL of 15% and 1000 mL of 20% EtOAc/hexane

Sources & evidence

ORD record
ord-5738c4642afe46eeb50cef88aee22323
Source dataset
uspto-grants-2008_12
Patent number
US07465726B2

Reaction notes

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