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Cesium carbonate → Toluene-4-sulfonic acid 4-[2-(4-chloro-phenyl)-4-oxo-6,7-dihydro-4H-thiazolo[5,4-c]pyridin-5-yl]-2-methoxy-phenyl ester

HRID 601524
Notes
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Reaction equation

HRID 601524 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:9][C:10]3[C:11](=[O:17])[NH:12][CH2:13][CH2:14][C:15]=3[N:16]=2)=[CH:4][CH:3]=1.Br[C:19]1[CH:24]=[CH:23][C:22]([O:25][S:26]([C:29]2[CH:34]=[CH:33][C:32]([CH3:35])=[CH:31][CH:30]=2)(=[O:28])=[O:27])=[C:21]([O:36][CH3:37])[CH:20]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.CCOC(C)=O.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]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:9][C:10]3[C:11](=[O:17])[N:12]([C:19]4[CH:24]=[CH:23][C:22]([O:25][S:26]([C:29]5[CH:30]=[CH:31][C:32]([CH3:35])=[CH:33][CH:34]=5)(=[O:28])=[O:27])=[C:21]([O:36][CH3:37])[CH:20]=4)[CH2:13][CH2:14][C:15]=3[N:16]=2)=[CH:4][CH:3]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 575017522-(4-Chloro-phenyl)-6,7-dihydro-5H-thiazolo[5,4-c]pyridin-4-oneHCID 866292054-Bromo-2-methoxyphenyl 4-methylbenzene-1-sulfonate

Product 1

HCID 57870236
Toluene-4-sulfonic acid 4-[2-(4-chloro-phenyl)-4-oxo-6,7-dihydro-4H-thiazolo[5,4-c]pyridin-5-yl]-2-methoxy-phenyl ester
Yield 60%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

Mix 2-(4-chloro-phenyl)-6,7-dihydro-5H-thiazolo[5,4-c]pyridin-4-one (128 mg, 0.48 mmol), toluene-4-sulfonic acid 4-bromo-2-methoxy-phenyl ester (218 mg, 0.61 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (17.2 mg, 0.030 mmol), Cs2CO3 (0.123 mg, 0.377 mmol) in dioxane (13 mL). Purge the solution with nitrogen for 30 min and then add tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (6.7 mg, 0.0073 mmol). Stir the mixture at reflux overnight, then cool to room temperature. Dilute the mixture with EtOAc (50 mL) and wash with water (2×30 mL) and brine (30 mL). Dry, filter and concentrate the organic solution and purify the residue by flash chromatography, using a linear gradient of 100% hexanes to 80% EtoAc/hexanes as eluent, to give the title compound as a light brown solid (155 mg, 60%). MS (ES+) 541.0 (M+1)+. 1H NMR (CDCl3): δ 7.92 (d, 2H, J=8.4 Hz), 7.78 (d, 2H, J=8.4 Hz), 7.44 (d, 2H, J=8.8 Hz), 7.31 (d, 2H, J=8.4 Hz), 7.17 (d, 1H, J=8.8 Hz), 6.96 (d, 1H, J=2.6 Hz), 6.82 (dd, 1H, J=8.6, 2.4 Hz), 4.11 (t, 2H, J=6.8 Hz), 3.57 (s, 3H), 3.28 (t, 2H, J=6.8 Hz), 2.44 (s, 3H).

Workup

  1. customPurge the solution with nitrogen for 30 min
  2. temperatureat reflux overnight
  3. washwash with water (2×30 mL) and brine (30 mL)
  4. customDry
  5. filtrationfilter
  6. concentrationconcentrate the organic solution
  7. custompurify the residue by flash chromatography

Sources & evidence

ORD record
ord-40fc9793b5224d79b718d05d1352515c
Source dataset
uspto-grants-2011_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07902356B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes