Tributylphosphine → HCID 59352438, compound

HRID 2385146Notes

Reaction equation

HRID 2385146 reaction equation
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]2([C:13]3=[CH:14][C:15]4[O:19][CH2:18][O:17][C:16]=4[CH:20]=[C:12]3[O:11][CH2:10]2)[C:2]1=[O:21].[CH3:22][C:23]1[O:24][C:25]([C:30]([F:33])([F:32])[F:31])=[C:26]([CH2:28]O)[N:27]=1.C(P(CCCC)CCCC)CCC>O1CCCC1>[CH3:22][C:23]1[O:24][C:25]([C:30]([F:33])([F:32])[F:31])=[C:26]([CH2:28][N:1]2[C:9]3[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=3)[C:3]3([C:13]4=[CH:14][C:15]5[O:19][CH2:18][O:17][C:16]=5[CH:20]=[C:12]4[O:11][CH2:10]3)[C:2]2=[O:21])[N:27]=1

Participants

5

Reactant 3

HCID 13831TributylphosphineHCID 53375495spiro[furo[2,3-f][1,3]benzodioxole-7,3'-indol]-2'(1'H)-oneHCID 67357008HCID 67357008, compound

Product 1

HCID 59352438HCID 59352438, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of spiro[furo[2,3-f][1,3]benzodioxole-7,3′-indol]-2′(1′H)-one (0.281 g, 1.0 mmol) and (2-methyl-5-(trifluoromethyl)oxazol-4-yl)methanol (0.18 g, 1.0 mmol) in anhydrous tetrahydrofuran (8 mL) was added tributylphosphine (0.30 g, 1.5 mmol) at 0° C., followed by additional of N,N,N′/N′-tetramethylazodicarboxamide (0.26 g, 1.5 mmol). The reaction mixture was stirred at 0° C. for 1 h and stirred at ambient temperature for 16 h. The reaction mixture was quenched with aqueous ammonium chloride (25%, 50 mL) and extracted with ethyl acetate (3×40 mL). The combined organic solution was washed with brine (30 mL), dried over anhydrous sodium sulfate and concentrated in vacuo to dryness. The residue was purified by column chromatography with ethyl acetate in hexanes (10% to 30% gradient) to give 1′-{[2-methyl-5-(trifluoromethyl)-1,3-oxazol-4-yl]methyl}spiro[furo[2,3-f][1,3]benzodioxole-7,3′-indol]-2′(1′H)-one (0.30 g, 68%) as a colorless solid: mp 136-137° C. (diethyl ether/hexane); 1H NMR (300 MHz, DMSO-d6) δ 7.32 (ddd, J=7.7, 1.2, 1.2 Hz, 1H), 7.19 (dd, J=7.6, 1.0 Hz, 1H), 7.07-7.03 (m, 2H), 6.70 (s, 1H), 6.29 (s, 1H), 5.93 (dd, J=5.0, 0.7 Hz, 2H), 4.98 (q, J=16.4 Hz, 2H), 4.75 (dd, J=20.8, 9.4 Hz, 2H), 2.46 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 176.5, 163.6, 155.1, 148.2, 141.9, 141.5, 137.6 (d, 3JCF=2.1 Hz), 133.5 (q, 2JCF=42.7 Hz), 131.6, 128.7, 123.5, 123.0, 119.8, 119.2 (q, 1JCF=266.9 Hz), 109.0, 103.0, 101.3, 93.1, 79.3, 57.2, 34.9, 13.4; MS (ES+) m/z 445.3 (M+1).

Workup

  1. stirringstirred at ambient temperature for 16 h
  2. customThe reaction mixture was quenched with aqueous ammonium chloride (25%, 50 mL)
  3. extractionextracted with ethyl acetate (3×40 mL)
  4. washThe combined organic solution was washed with brine (30 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo to dryness
  7. customThe residue was purified by column chromatography with ethyl acetate in hexanes (10% to 30% gradient)

Sources & evidence

ORD record
ord-b941f05c9fc24fbfa0f12b2fc22b80a3
Source dataset
uspto-grants-2012_09
Patent number
US08263606B2

Reaction notes

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