Potassium Carbonate → HCID 67199079, compound

HRID 552020Notes

Reaction equation

HRID 552020 reaction equation
[CH3:1][CH:2]([CH2:4][CH2:5][CH2:6][C@H:7]([C@@H:9]1[C@:26]2([CH3:27])[C@H:12]([C@H:13]3[C@H:23]([CH2:24][CH2:25]2)[C@:21]2([CH3:22])[C:16]([CH2:17][C@@H:18]([NH:28]CCCNC(=O)CCNC(=O)CCNC(=O)CCCCCNC4C=CC([N+]([O-])=O)=CC=4[N+]([O-])=O)[CH2:19][CH2:20]2)=[CH:15][CH2:14]3)[CH2:11][CH2:10]1)[CH3:8])[CH3:3].Br[CH2:64][CH2:65][CH2:66][CH2:67][C:68]([O:70][CH2:71][CH3:72])=[O:69].C([O-])([O-])=O.[K+].[K+].CC(OC(O[C:87]([O:89][C:90]([CH3:93])([CH3:92])[CH3:91])=[O:88])=O)(C)C.CCN(C(C)C)C(C)C>CN(C=O)C>[C:90]([O:89][C:87]([N:28]([C@H:18]1[CH2:19][CH2:20][C@@:21]2([CH3:22])[C:16](=[CH:15][CH2:14][C@@H:13]3[C@@H:23]2[CH2:24][CH2:25][C@@:26]2([CH3:27])[C@H:12]3[CH2:11][CH2:10][C@@H:9]2[C@H:7]([CH3:8])[CH2:6][CH2:5][CH2:4][CH:2]([CH3:3])[CH3:1])[CH2:17]1)[CH2:64][CH2:65][CH2:66][CH2:67][C:68]([O:70][CH2:71][CH3:72])=[O:69])=[O:88])([CH3:91])([CH3:92])[CH3:93]

Participants

7

Reactant 5

HCID 11430Potassium CarbonateHCID 81531DiisopropylethylamineHCID 84580Ethyl 5-bromovalerateHCID 90495Di-tert-butyl dicarbonateHCID 86608456HCID 86608456, compound

Product 1

HCID 67199079HCID 67199079, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To DMF (10 mL) was added 3β-amino-5-cholestene (2, 386 mg, 1.0 mmol),1 ethyl 5-bromovalerate (174 μL, 1.1 mmol) and K2CO3 (276 mg, 2.0 mmol). The solution was heated to 60° C. and stirred for 24 h. The reaction was cooled to 23° C. and DMF was removed in vacuo. To the resulting solid residue was added CH2Cl2 (10 mL), insoluble salts were removed by filtration, and solids were washed with additional CH2Cl2 (5 mL). To this solution containing the crude secondary amine product was added (Boc)2O (327 mg, 1.5 mmol) and DIEA (0.5 mL, 3.0 mmol). The reaction was stirred for 3 h at 23° C. and concentrated in vacuo. Flash column chromatography (hexanes/ethyl acetate, 10:1) afforded 3 (417 mg, 68%) as a white solid, mp 78-79° C.; 1H NMR (400 MHz, CDCl3) δ 5.30 (d, 1H), 4.10 (q, J=7.1 Hz, 2H), 3.73 (br s, 1H), 3.09 (br s, 2H), 2.30 (t, J=7.1 Hz, 2H), 2.01-0.83 (m, 56H), 0.66 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 173.6, 155.5, 141.3, 121.4, 79.3, 60.4, 56.9, 56.3 (×2), 50.3, 42.6 (×2), 39.9, 39.7, 38.6, 37.1, 36.8, 36.3, 35.9, 34.2, 32.0 (×2), 28.7 (Boc Me3), 28.4, 28.1 (×2), 26.9, 24.4, 24.0, 23.0, 22.7, 22.6, 21.2, 19.6, 18.9, 14.4, 12.0; IR (film) ν max 2935, 2867, 1737, 1692, 1466, 1409, 1365, 1247, 1173 cm−1; CI m/z 614.5146 (MH+, C39H68NO4 requires 614.5148).

Workup

  1. temperatureThe reaction was cooled to 23° C.
  2. customDMF was removed in vacuo
  3. additionTo the resulting solid residue was added CH2Cl2 (10 mL), insoluble salts
  4. customwere removed by filtration, and solids
  5. washwere washed with additional CH2Cl2 (5 mL)
  6. additionTo this solution containing the crude secondary amine product
  7. stirringThe reaction was stirred for 3 h at 23° C.
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0829a78dff494d39a78cb0b36a3a793b
Source dataset
uspto-grants-2011_05
Patent number
US07947647B2

Reaction notes

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