Morpholine → HCID 12000045, compound

HRID 1008246Notes

Reaction equation

HRID 1008246 reaction equation
C(OC(=O)[NH:6][C@@H:7]([CH2:20][C:21]1[CH:26]=[CH:25][C:24]([O:27]CC=C)=[CH:23][CH:22]=1)[CH2:8][O:9][Si:10]([CH:17]([CH3:19])[CH3:18])([CH:14]([CH3:16])[CH3:15])[CH:11]([CH3:13])[CH3:12])C=C.N1CCOCC1>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:6][C@H:7]([CH2:8][O:9][Si:10]([CH:17]([CH3:19])[CH3:18])([CH:11]([CH3:13])[CH3:12])[CH:14]([CH3:16])[CH3:15])[CH2:20][C:21]1[CH:26]=[CH:25][C:24]([OH:27])=[CH:23][CH:22]=1

Participants

5

Reactant 2

HCID 8083MorpholineHCID 60111295HCID 60111295, compound

Product 1

HCID 12000045HCID 12000045, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
47 °C

Procedure

To a solution of 21 (6.05 g, 13.5 mmol, 1.0 equiv) in THF (135 mL) at room temperature, was added morpholine (11.8 mL, 135.6 mmol, 10 equiv), then tetrakis(triphenylphosphine)palladium(0) (1.56 g, 1.35 mmol, 0.1 equiv) in the dark. The solution was warmed to 47° C. The reaction was stirred at 47° C. for 10 hours, after which time the solution was cooled to room temperature and the THF was removed under reduced pressure. Purification by flash chromatography (30% EtOAc/hexane→100% EtOAc) afforded 22 (3.9 g, 90%) as a brown solid with a minor amount of Ph3PO. Rf=0.2 (EtOAc); FTIR (film, cm−1) 2938, 2866, 1515, 1462, 1251, 1105; 1H NMR (500 MHz, CDCl3) δ7.01 (d, J=8.5 Hz, 2H), 6.71 (d, J=8.5 Hz, 2H), 4.5 (br s, 2H), 3.75 (dd, J=10.0, 3.5 Hz, 1H), 3.61, (dd, J=9.5, 6.5 Hz, 1H), 3.19 (br s, 1H), 2.79 (dd, J=13.3, 6.0 Hz, 1H), 2.64 (dd, J=13.8, 7.5 Hz, 1H), 1.05 (m, 21H); 13C NMR (100 MHz, CDCl3) δ155.1, 130.3, 129.1, 115.8, 115.6, 66.2, 54.9, 37.9, 18.1, 11.9; HRMS (ES+) calculated for C18H33NO2Si (M+H)+: 324.2281, found: 324.2374.

Workup

  1. temperatureafter which time the solution was cooled to room temperature
  2. customthe THF was removed under reduced pressure
  3. customPurification by flash chromatography (30% EtOAc/hexane→100% EtOAc)

Sources & evidence

ORD record
ord-0bef73143b854799bfdf12d1a0034b74
Source dataset
uspto-grants-2004_09
Patent number
US06797819B1

Reaction notes

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