Sodium Carbonate → HCID 67972151, compound

HRID 331401Notes

Reaction equation

HRID 331401 reaction equation
Br[C:2]1[C:7]2[CH:8]=[CH:9][O:10][C:6]=2[C:5]([F:11])=[CH:4][CH:3]=1.CC1(C)C(C)(C)OB([C:20]2[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:22][CH:21]=2)O1.C(=O)([O-])[O-].[Na+].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>COCCOC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:29]([O:28][C:26]([N:23]1[CH2:22][CH:21]=[C:20]([C:2]2[C:7]3[CH:8]=[CH:9][O:10][C:6]=3[C:5]([F:11])=[CH:4][CH:3]=2)[CH2:25][CH2:24]1)=[O:27])([CH3:32])([CH3:30])[CH3:31]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 668005644-bromo-7-fluorobenzofuran

Product 1

HCID 67972151HCID 67972151, compoundYield 91.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of commercially available 4-bromo-7-fluoro-benzofurane [CAS-No 1194376-46-9] (0.72 g, 3.35 mmol) and commercially available tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (1.09 g, 3.52 mmol) in 1,2-dimethoxyethane (22 ml) and 2M sodium carbonate solution (5.58 ml, 11.2 mmol) was purged with argon in an ultrasonic bath during 5 min. Then triphenylphosphine (176 mg, 0.67 mmol) and palladium(II)acetate (75.2 mg, 0.34 mmol) were added and the reaction mixture was allowed to stir at 85° C. for 5 h. The reaction mixture was cooled to room temperature, poured into water (50 ml) and extracted with diethyl ether (2×120 ml). The combined organic layers were washed with brine (50 ml), dried (MgSO4) and evaporated. The crude product (1.7 g) was further purified by flash chromatography on silica gel (heptane/ethyl acetate, 0-50%) to yield 4-(7-fluoro-benzofuran-4-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester as a yellow oil (0.97 g, 91%), MS (ISP) m/z=262.1 [(M+H)+].

Workup

  1. customwas purged with argon in an ultrasonic bath during 5 min
  2. temperatureThe reaction mixture was cooled to room temperature
  3. extractionextracted with diethyl ether (2×120 ml)
  4. washThe combined organic layers were washed with brine (50 ml)
  5. dry with materialdried (MgSO4)
  6. customevaporated
  7. customThe crude product (1.7 g) was further purified by flash chromatography on silica gel (heptane/ethyl acetate, 0-50%)

Sources & evidence

ORD record
ord-f644b112c4b54ef6ac4e722e294209ee
Source dataset
uspto-grants-2014_11
Patent number
US08877778B2

Reaction notes

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