Cesium carbonate → (5R)-5-(2,2-Dimethyl-4H-1,3-benzodioxin-6-yl)-3-{6-[2-({4-[(diphenylmethylene)amino]benzyl}oxy)ethoxy]hexyl}-1,3-oxazolidin-2-one

HRID 2369709Notes

Reaction equation

HRID 2369709 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[C:53](=[NH:66])([C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)[C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1.Br[C:68]1[CH:102]=[CH:101][C:71]([CH2:72][O:73][CH2:74][CH2:75][O:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][N:83]2[CH2:87][C@@H:86]([C:88]3[CH:99]=[CH:98][C:91]4[O:92][C:93]([CH3:97])([CH3:96])[O:94][CH2:95][C:90]=4[CH:89]=3)[O:85][C:84]2=[O:100])=[CH:70][CH:69]=1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.ClCCl>[CH3:96][C:93]1([CH3:97])[O:92][C:91]2[CH:98]=[CH:99][C:88]([C@H:86]3[O:85][C:84](=[O:100])[N:83]([CH2:82][CH2:81][CH2:80][CH2:79][CH2:78][CH2:77][O:76][CH2:75][CH2:74][O:73][CH2:72][C:71]4[CH:70]=[CH:69][C:68]([N:66]=[C:53]([C:60]5[CH:61]=[CH:62][CH:63]=[CH:64][CH:65]=5)[C:54]5[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=5)=[CH:102][CH:101]=4)[CH2:87]3)=[CH:89][C:90]=2[CH2:95][O:94]1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 66845394(5R)-3-(6-{2-[(4-bromobenzyl)oxy]ethoxy}hexyl)-5-(2,2-dimethyl4H-1,3-benzodioxin-6-yl)-1,3-oxazolidin-2-one

Product 1

HCID 86597512(5R)-5-(2,2-Dimethyl-4H-1,3-benzodioxin-6-yl)-3-{6-[2-({4-[(diphenylmethylene)amino]benzyl}oxy)ethoxy]hexyl}-1,3-oxazolidin-2-one

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent2×HCID 6344DichloromethaneSolvent

Procedure

A mixture of palladium (II) acetate (40 mg), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (166 mg) and cesium carbonate (811 mg) under nitrogen was treated with toluene (15 ml) and benzophenone imine (0.36 ml) followed by a solution of (5R)-3-(6-{2-[(4-bromobenzyl)oxy]ethoxy}hexyl)-5-(2,2-dimethyl4H-1,3-benzodioxin-6-yl)-1,3-oxazolidin-2-one (1.00 g) in toluene (10 ml). The stirred mixture was heated to 100° for 18 h. The mixture was cooled to 20°, dichloromethane (25 ml) was added and the mixture was filtered. The filtrate was evaporated in vacuo and the residue purified by chromatography on flash silica gel (30 mm diameter column). Elution with EtOAc-PE (3:2) gave the title compound (890 mg). LCMS RT=4.07 min.

Workup

  1. temperatureThe stirred mixture was heated to 100° for 18 h
  2. temperatureThe mixture was cooled to 20°
  3. filtrationthe mixture was filtered
  4. customThe filtrate was evaporated in vacuo
  5. customthe residue purified by chromatography on flash silica gel (30 mm diameter column)
  6. washElution with EtOAc-PE (3:2)

Sources & evidence

ORD record
ord-7e7789aaf9d7450fbe3e9bc17f54f1d3
Source dataset
uspto-grants-2014_04
Patent number
USRE044874E1

Reaction notes

Loading…