HCID 89955707, compound → HCID 89955554, compound

HRID 1481272Notes

Reaction equation

HRID 1481272 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:13]1[CH:18]=[C:17]([C:19]2[CH:24]=[CH:23][C:22]([NH:25][C:26](=[O:29])[O:27][CH3:28])=[CH:21][C:20]=2[NH:30][C:31](=[O:36])[C@H:32]([CH3:35])[CH:33]=[CH2:34])[CH:16]=[CH:15][N:14]=1)[CH2:10]C=C)=[O:7])([CH3:4])([CH3:3])[CH3:2]>C(Cl)Cl.Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1>[C:1]([O:5][C:6]([NH:8][C@@H:9]1[C:13]2[CH:18]=[C:17]([CH:16]=[CH:15][N:14]=2)[C:19]2[CH:24]=[CH:23][C:22]([NH:25][C:26](=[O:29])[O:27][CH3:28])=[CH:21][C:20]=2[NH:30][C:31](=[O:36])[C@H:32]([CH3:35])[CH:33]=[CH:34][CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 1

HCID 89955707HCID 89955707, compound

Product 1

HCID 89955554HCID 89955554, compoundYield 71.2%

Reagents, catalysts & solvents 2

HCID 178425456HCID 178425456, compoundCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a RBF was added 1G (0.5 g, 1.011 mmol), pTsOH monohydrate (0.212 g, 1.112 mmol), and dichloromethane (84 ml). The flask was equipped with a reflux condensor and the clear yellow solution was degassed with argon for 30 min. The reaction was then warmed to reflux for 1 h. Then a solution of Grubbs II (0.172 g, 0.202 mmol) in DCM (2 mL) was added dropwise to the reaction mixture. After 4 h at reflux, the reaction was cooled to rt, washed with sat. Na2CO3, brine, dried over MgSO4, filtered, and concentrated to give a brown solid. The crude product was then purified using silica gel chromatography to give 1H (0.336 g, 71.2% yield) as a yellow solid. 1H NMR (500 MHz, METHANOL-d4) δ 8.52 (d, J=5.2 Hz, 1H), 7.54 (d, J=1.4 Hz, 1H), 7.48-7.43 (m, 1H), 7.38 (d, J=8.3 Hz, 1H), 7.24 (dd, J=5.1, 1.5 Hz, 1H), 6.89 (s, 1H), 5.75-5.65 (m, 1H), 4.60 (dd, J=11.3, 3.6 Hz, 1H), 4.39 (dd, J=15.1, 9.6 Hz, 1H), 3.75 (s, 3H), 3.14-3.06 (m, 1H), 2.75-2.68 (m, 1H), 2.04-1.94 (m, 1H), 1.44 (s, 9H), 1.30 (br. s., 1H), 1.04 (d, J=6.6 Hz, 3H). MS (ESI) m/z: 467.2 (M+H)+.

Workup

  1. customThe flask was equipped with a reflux condensor
  2. customthe clear yellow solution was degassed with argon for 30 min
  3. temperatureThe reaction was then warmed
  4. temperatureto reflux for 1 h
  5. temperatureAfter 4 h at reflux
  6. washwashed with sat. Na2CO3, brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give a brown solid
  11. customThe crude product was then purified

Sources & evidence

ORD record
ord-387f650d6fdd4fe9a300548e42273601
Source dataset
uspto-grants-2016_08
Patent number
US09409908B2

Reaction notes

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