Pent-4-ynoic acid butyl ester → 5-[6-(4-Methoxy-benzylamino)-pyridin-2-yl]-pent-4-ynoic acid butyl ester

HRID 2120664Notes

Reaction equation

HRID 2120664 reaction equation
Br[C:2]1[N:7]=[C:6]([NH:8][CH2:9][C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=2)[CH:5]=[CH:4][CH:3]=1.[CH2:18]([O:22][C:23](=[O:28])[CH2:24][CH2:25][C:26]#[CH:27])[CH2:19][CH2:20][CH3:21]>CCN(CC)CC.[Cu]I>[CH2:18]([O:22][C:23](=[O:28])[CH2:24][CH2:25][C:26]#[C:27][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]([NH:8][CH2:9][C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=2)[N:7]=1)[CH2:19][CH2:20][CH3:21]

Participants

5

Reactant 2

HCID 23435506Pent-4-ynoic acid butyl esterHCID 234355096-Bromo-(4-methoxybenzylamino)pyridine

Product 1

HCID 696660335-[6-(4-Methoxy-benzylamino)-pyridin-2-yl]-pent-4-ynoic acid butyl esterYield 79.6%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8471TriethylamineSolvent

Procedure

To a mixture of 6-2 (8.64 g, 29.48 mmol) and 6-4 (5.0 g, 32.4 mmol) in Et3N (50 mL) at 0° was added CuI (0.14 g, 0.74). The solution was purged with argon and [(C6H5)3P]2PdCl2 (0.52 g, 0.74 mmol) was added. After 1 h the cooling bath was removed and the solution was stirred for an additional 12 h. The solution was diluted with diethyl ether (250 mL) and washed with water (4×100 ml) followed by brine (100 mL). The etheral layer was dried (Na2SO4), concentrated, and chromatographed (silica gel, 30% ethyl acetate/hexanes) to give 8.6 g of 6-5.

Workup

  1. additionwas added
  2. customAfter 1 h the cooling bath was removed
  3. additionThe solution was diluted with diethyl ether (250 mL)
  4. washwashed with water (4×100 ml)
  5. dry with materialThe etheral layer was dried (Na2SO4)
  6. concentrationconcentrated
  7. customchromatographed (silica gel, 30% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-79c0443949284053a7658ea67212914b
Source dataset
uspto-grants-2004_02
Patent number
US06693101B2

Reaction notes

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