Triethylamine → HCID 67352364, compound

HRID 1669499Notes

Reaction equation

HRID 1669499 reaction equation
[CH3:1][O:2][C:3](=[O:21])[C@@H:4]([CH2:13][C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=1)[NH:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7].[O:22]([C:29]1[CH:34]=[CH:33][C:32](B(O)O)=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C(N(CC)CC)C>ClCCl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH3:1][O:2][C:3](=[O:21])[C@H:4]([NH:5][C:6]([O:8][C:9]([CH3:12])([CH3:10])[CH3:11])=[O:7])[CH2:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][C:32]2[CH:33]=[CH:34][C:29]([O:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[CH:30][CH:31]=2)=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 27343774-Phenoxyphenylboronic acidHCID 7016055Boc-D-Tyr-OMe

Product 1

HCID 67352364HCID 67352364, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of Boc-D-Tyrosine-Methyl ester (0.950 g, 3.217 mmol), 4-Phenoxyphenyl-boronic acid (0.688 g, 3.217 mmol), and triethylamine (228 mL, 16.083 mmol) in anhydrous dichloromethane (DCM) (79.2 mL) at room temperature under an atmosphere of nitrogen was added copper (II) acetate (0.445 g, 3.217 mmol), and the resulting mixture was stirred at room temperature for about 42 hours. The reaction mixture was washed with 60 mL of water and 20 mL of DCM and filtered. The DCM layer was then extracted. The aqueous layer was re-extracted with DCM (2×30 mL). The organic layers were combined, washed with 60 mL of brine, and seperated. Organic layer was dried over anhydrous Na2SO4, filtered, and the solvent was removed in vacuo to obtain the crude mixture, which was purified by silica gel flash chromatography, using EtOAc/hexane (gradient system), to obtain the product (0.57 g, 50%): 1H NMR (400 MHz, CDCL3): δ 1.42 (s, 9H), 1.59 (s, 1H), 2.99-3.11 (m, 2H), 3.67-3.73 (m, 3H), 4.57 (d, 1H, J=7.2 Hz), 4.99 (d, 1H, J=8 Hz), 6.92 (d, 2H, J=8.8 Hz), 6.99-7.01 (m, 5H), 7.07-7.10 (m, 3H), 7.31-7.35 (m, 2H).

Workup

  1. washThe reaction mixture was washed with 60 mL of water and 20 mL of DCM
  2. filtrationfiltered
  3. extractionThe DCM layer was then extracted
  4. extractionThe aqueous layer was re-extracted with DCM (2×30 mL)
  5. washwashed with 60 mL of brine
  6. customseperated
  7. dry with materialOrganic layer was dried over anhydrous Na2SO4
  8. filtrationfiltered
  9. customthe solvent was removed in vacuo
  10. customto obtain the crude mixture, which
  11. customwas purified by silica gel flash chromatography

Sources & evidence

ORD record
ord-6ae3064b560e4b688e33461bda03ff29
Source dataset
uspto-grants-2011_08
Patent number
US07989480B2

Reaction notes

Loading…