Cesium carbonate → HCID 59895730, compound

HRID 2185618Notes

Reaction equation

HRID 2185618 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:13]=[C:12]([C@H:14]([OH:19])[C:15]([CH3:18])([CH3:17])[CH3:16])[CH:11]=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:27][CH2:28][O:29][Si](C(C)(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1.C(OCC)(=O)C.C(#N)C>[OH:29][CH2:28][CH2:27][O:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[N:13]=[C:12]([C@H:14]([OH:19])[C:15]([CH3:16])([CH3:18])[CH3:17])[CH:11]=[CH:10][CH:9]=2)=[CH:6][CH:7]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 2724141Tetrabutylammonium FluorideHCID 3608067(2-Bromoethoxy)-tert-butyldimethylsilaneHCID 136383541HCID 136383541, compound

Product 1

HCID 59895730HCID 59895730, compoundYield 83%

Reagents, catalysts & solvents 3

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A dry 250 mL three-necked flask was charged with (R)-1-[6-(4-hydroxyphenyl)pyridin-2-yl]-2,2-dimethylpropanol (4b) (2.54 g, 9.9 mmol), cesium carbonate (6.43 g, 19.8 mmol) and 100 mL of acetonitrile. Next, 2-bromoethyl-tert-butyldimethylsilyl ether was added through a dropping funnel. The mixture was heated under reflux for 2 hours and stirred for additional 14 hours at room temperature. After standard work-up with ethyl acetate the crude product was dissolved in 25 mL of THF and 11 mL of TBAF (1 M in THF) were added. After stirring for 1 hour at room temperature, the solution was quenched with 50 mL of water and standard work-up with dichloromethane followed by column chromatography (SiO2, eluent: ethyl acetate/hexanes=1:1) yielded 2.46 g (83%) of (5) as a white powder. Mp: 104° C. [a]D,=−14.4 ©=2.28, acetone). 1H NMR (300 MHZ, CDCl3): δ0.96 (s, 9H); 2.36-2.40 (m, 1H); 3.95-4.01 (m, 2H); 4.11-4.15 (m, 2H); 4.39 (d, J=7.4 Hz, 1H); 4.66 (d, J=7.4 Hz, 1H); 7.01 (d, J=8.8 Hz, 2H); 7.06 (dd, J=7.97 Hz, 0.8 Hz, 1H); 7.57 (dd, J=7.97 Hz, 0.8 Hz, 1H); 7.66 (m, 1H); 7.95 (d, J=8.8 Hz, 2H). 13C NMR (75 MHZ, CDCl3): δ26.0; 36.3; 61.4; 69.4; 80.2; 114.7; 118.2; 120.7; 128.2; 131.9; 136.4; 155.0; 159.3; 159.7. M S 70 eV):m/z(%)301(M, 7),244 (100).IR(KBr): 1608, 1576, 1516, 1453, 1255, 1174, 1046, 812 cm−1. Anal. Calcd. for C18H23NO3: C, 71.73; H, 7.69; N, 4.65. Found: C, 71.59; H, 7.68; N, 4.56.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 2 hours
  3. stirringAfter stirring for 1 hour at room temperature
  4. customthe solution was quenched with 50 mL of water and standard work-up with dichloromethane

Sources & evidence

ORD record
ord-ac133fbfda994a79b7721bcfec807bd7
Source dataset
uspto-grants-2002_06
Patent number
US06403522B1

Reaction notes

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