Triethylamine → Methyl 4-[3-[[(1,1-dimethylethoxy)carbonyl]amino]-1-propyn-1-yl]benzoate

HRID 2221448Notes

Reaction equation

HRID 2221448 reaction equation
[C:1]([NH:8][CH2:9][C:10]#[CH:11])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].I[C:13]1[CH:22]=[CH:21][C:16]([C:17]([O:19][CH3:20])=[O:18])=[CH:15][CH:14]=1.C(N(CC)CC)C>CN(C=O)C.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:1]([NH:8][CH2:9][C:10]#[C:11][C:13]1[CH:22]=[CH:21][C:16]([C:17]([O:19][CH3:20])=[O:18])=[CH:15][CH:14]=1)([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 69273Methyl 4-iodobenzoateHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamate

Product 1

HCID 18617679Methyl 4-[3-[[(1,1-dimethylethoxy)carbonyl]amino]-1-propyn-1-yl]benzoateYield 88.7%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of N-Boc propargylamine (2.07 g, 13.4 mmol), methyl 4-iodobenzoate (3.50 g, 13.4 mmol) and PdCl2(PPh3)2 (0.938 g, 1.34 mmol) in DMF (20 ml) was added triethylamine (9.31 ml, 126 mmol). The reaction mixture was stirred for 30 min at room temperature. Cu(I)I (0.508 g, 2.67 mmol) was added and stirring was continued for additional 16 h. The reaction mixture was diluted with ethyl acetate (250 ml), washed with 0.5M aqueous HCl (200 ml), and finally with brine (200 ml). The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo. Purification by flash chromatography over silica gel with ethyl acetate/hexane (1/4) provided methyl 4-(N-Boc-3-aminoprop-1-ynyl)benzoate (3.44 g) as highly viscous oil.

Workup

  1. stirringstirring
  2. waitwas continued for additional 16 h
  3. washwashed with 0.5M aqueous HCl (200 ml)
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash chromatography over silica gel with ethyl acetate/hexane (1/4)

Sources & evidence

ORD record
ord-f85f23f4cf24434c87ddfd24a2793347
Source dataset
uspto-grants-2008_05
Patent number
US07368572B2

Reaction notes

Loading…