Triphenylphosphine → HCID 60170764, compound

HRID 1817765Notes

Reaction equation

HRID 1817765 reaction equation
[F:1][C:2]([F:25])([F:24])[S:3]([O:6][C:7]1[NH:11][N:10]=[C:9]([C:12]2[CH:21]=[CH:20][C:19]3[C:14](=[CH:15][CH:16]=[C:17]([O:22][CH3:23])[CH:18]=3)[CH:13]=2)[CH:8]=1)(=[O:5])=[O:4].O[CH:27]([C:29]1[CH:46]=[CH:45][C:32]([C:33]([NH:35][CH2:36][CH2:37][C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])=[O:34])=[CH:31][CH:30]=1)[CH3:28].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C(Cl)Cl>[CH3:23][O:22][C:17]1[CH:18]=[C:19]2[C:14](=[CH:15][CH:16]=1)[CH:13]=[C:12]([C:9]1[CH:8]=[C:7]([O:6][S:3]([C:2]([F:1])([F:24])[F:25])(=[O:5])=[O:4])[N:11]([CH:27]([C:29]3[CH:46]=[CH:45][C:32]([C:33]([NH:35][CH2:36][CH2:37][C:38]([O:40][C:41]([CH3:43])([CH3:42])[CH3:44])=[O:39])=[O:34])=[CH:31][CH:30]=3)[CH3:28])[N:10]=1)[CH:21]=[CH:20]2

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 67482540HCID 67482540, compoundHCID 178487403HCID 178487403, compound

Product 1

HCID 60170764HCID 60170764, compoundYield 30.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

3-(6-Methoxy-2-naphthyl)-1H-pyrazol-5-yl trifluoromethanesulfonate (1.36 g, 3.65 mmol), tert-butyl N-[4-(1-hydroxyethyl)benzoyl]-β-alaninate (1.2 g, 4.02 mmol), and triphenylphosphine (1.44 g, 5.48 mmol) were suspended in DCM (25 ml). Diisopropyl azodicarboxylate (0.87 ml, 4.38 mmol) was added slowly. The mixture was stirred for 2 hr and then concentrated to ˜10 ml. This residue was chromatographed (SiO2, 25-30% ethyl acetate gradient) to give 0.727 g of tert-butyl N-{4-[1-(3-(6-methoxy-2-naphthyl)-5-{[(trifluoromethyl)sulfonyl]oxy}-1H-pyrazol-1-yl)ethyl]benzoyl}-β-alaninate, NMR (500 MHz, CDCl3) δ: 1.45 (s, 9H); 2.01 (d, J=7.1 Hz, 3H); 2.53 (t, J=5.9 Hz, 2H); 3.67 (q, J=5.9 Hz, 2H); 3.94 (s, 3H); 5.56 (q, J=7.1 Hz, 1H); 6.54 (s, 1H); 6.78 (br, 1H); 7.16 (br, 1H); 7.17 (dd, J=2.6 Hz, 9 Hz, 1H); 7.41 (d, J=8.4 Hz, 2H); 7.74 (d, J=8.4 Hz, 2H); 7.78 (d, J=8.4 Hz, 1H); 7.79 (d, J=8.5 Hz, 1H); 7.93 (dd, J=1.8 Hz, 8.5 Hz, 1H); 8.14 (d, J=1.6 Hz, 1H). MS C31H32F3N3O7S Cald: 647.19; Obsd (M+Na): 670.02 and 1.165 g of tert-butyl N-{4-[1-(5-(6-methoxy-2-naphthyl)-3-{[(trifluoromethyl)sulfonyl]oxy}-1H-pyrazol-1-yl)ethyl]benzoyl}-β-alaninate. NMR (500 MHz, CDCl3) δ: 1.46 (s, 9H); 1.85 (d, J=7.1 Hz, 3H); 2.55 (t, J=5.8 Hz, 2H); 3.68 (q, J=5.8 Hz, 2H); 3.95 (s, 3H): 5.52 (q, J=7.1 Hz, 1H); 6.23 (s, 1H); 6.85 (br, 1H); 7.16 (d, J=2.6 Hz, 1H); 7.21 (dd, J=2.6 Hz, 8.7 Hz, 1H); 7.22 (d, J=8.4 Hz, 2H); 7.24 (dd, J=1.5 Hz, 8.4 Hz, 1H); 7.62 (d, J=1.5 Hz, 1H); 7.67 (d, J=8.7 Hz, 1H); 7.71 (d, J=8.3 Hz, 2H); 7.76 (d, J=8.4 Hz, 1H). MS C31H32F3N3O7S Cald: 647.19; Obsd (M+Na): 670.20.

Workup

  1. concentrationconcentrated to ˜10 ml
  2. customThis residue was chromatographed (SiO2, 25-30% ethyl acetate gradient)

Sources & evidence

ORD record
ord-291a00a05d814ddb99289e6f208a36a0
Source dataset
uspto-grants-2009_10
Patent number
US07598285B2

Reaction notes

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