Cesium carbonate → HCID 69358469, compound

HRID 852653Notes

Reaction equation

HRID 852653 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([N+:12]([O-:14])=[O:13])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].C([O-])([O-])=O.[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.[C:63]1([CH:69]2[CH2:74][CH2:73][S:72](=[O:76])(=[O:75])[NH:71][CH2:70]2)[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[O:75]=[S:72]1(=[O:76])[CH2:73][CH2:74][CH:69]([C:63]2[CH:64]=[CH:65][CH:66]=[CH:67][CH:68]=2)[CH2:70][N:71]1[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([N+:12]([O-:14])=[O:13])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 239341Methyl 3-bromo-5-nitrobenzoateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 68463624HCID 68463624, compound

Product 1

HCID 69358469HCID 69358469, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A flask was charged under nitrogen with methyl 3-bromo-5-nitrobenzoate (D11) (136 mg, 0.52 mmol, 1,1 equiv), Cs2CO3 (216 mg, 0.66 mmol, 1.4 equiv), tris(dibenzylideneacetone)dipalladium(0) (22 mg, 0.023 mmol, 0.05 equiv), Xantphos (27 mg, 0.047 mmol, 0.1 equiv) and toluene (10 ml). 4-phenyltetrahydro-2H-1,2-thiazine 1,1-dioxide (J. Morris, D. G. Wishka J. Org. Chem. 1991, 56, 3549-3556, 100 mg, 0.47 mmol, 1 equiv) was then added and the resulting mixture was stirred at 120° C. for 5 h then cooled to room temperature and concentrated in vacuo. The residue was partitioned between H2O and AcOEt and the aqueous phase was re-extracted with AcOEt. The combined organic solutions were dried over MgSO4 and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (iso-hexane/AcOEt: 7/3) gave methyl 3-(1,1-dioxido-4-phenyltetrahydro-2H-1,2-thiazin-2-yl)-5-nitrobenzoate (B123) (110 mg, 60%) as a yellow oil. [M+H+ NH3]+=408.3, RT=3.24 min

Workup

  1. temperaturethen cooled to room temperature
  2. concentrationconcentrated in vacuo
  3. customThe residue was partitioned between H2O and AcOEt
  4. extractionthe aqueous phase was re-extracted with AcOEt
  5. dry with materialThe combined organic solutions were dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customPurification of the residue by flash chromatography on silica gel (iso-hexane/AcOEt: 7/3)

Sources & evidence

ORD record
ord-6d8aca27b4a64d7ebe0a8096a8a83155
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Reaction notes

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