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Lithium Chloride → ethyl 5-(4-(4-chlorobenzyl)-2-(pyridin-4-yl)thiazol-5-yl)-1H-pyrazole-3-carboxylate

HRID 2402099
Notes
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Reaction equation

HRID 2402099 reaction equation
Br[C:2]1[S:6][C:5]([C:7]2[CH:12]=[CH:11][N:10]=[CH:9][CH:8]=2)=[N:4][C:3]=1[CH2:13][C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=1.C([Sn](CCCC)(CCCC)[C:26]1[NH:30][N:29]=[C:28]([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH:27]=1)CCC.[Cl-].[Li+]>O1CCOCC1.C(OCC)(=O)C.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.[Cu]I>[Cl:20][C:17]1[CH:18]=[CH:19][C:14]([CH2:13][C:3]2[N:4]=[C:5]([C:7]3[CH:12]=[CH:11][N:10]=[CH:9][CH:8]=3)[S:6][C:2]=2[C:26]2[NH:30][N:29]=[C:28]([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH:27]=2)=[CH:15][CH:16]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 3

HCID 433294Lithium ChlorideHCID 149720685-Tributylstannyl-1H-pyrazole-3-carboxylic acid ethyl esterHCID 667479255-Bromo-4-(4-chlorobenzyl)-2-(pyridin-4-yl)thiazole

Product 1

HCID 66749559ethyl 5-(4-(4-chlorobenzyl)-2-(pyridin-4-yl)thiazol-5-yl)-1H-pyrazole-3-carboxylateYield 12.2%

Reagents, catalysts & solvents 4

HCID 24350
Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)
Catalyst
HCID 178418397HCID 178418397, compoundCatalyst
HCID 8857Ethyl AcetateSolvent
HCID 312751,4-DioxaneSolvent

Procedure

An argon degassed mixture of 5-bromo-4-(4-chlorobenzyl)-2-(pyridin-4-yl)thiazole (583 mg, 1.59 mmol), ethyl 5-(tributylstannyl)-1H-pyrazole-3-carboxylate (456 mg, 1.06 mmol), tetrakis(triphenylphosphine)palladium(0) (61.4 mg, 0.0531 mmol), copper(I) iodide (60.7 mg, 0.319 mmol), and lithium chloride (135 mg, 3.19 mmol) in dioxane (7.46 mL) was heated in a microwave at 150 degrees for 30 minutes. The reaction mixture was slurried in ethyl acetate (100 mL) and water (2 mL) and the mixture was filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (EA/DCM=0/100→100/0) to give the crude product. This material was purified by preparative reverse phase chromatography to give 55 mg (12% yield) of the title compound as a white solid. LC/MS (FA) ES+ 425, 427. 1H NMR (300 MHz, DMSO-d6) δ: 8.71-8.69 (m, 2H), 7.85-7.83 (m, 2H), 7.36-7.33 (m, 2H), 7.28-7.25 (m, 2H), 7.09 (s, 1H), 4.41 (s, 2H), 4.34 (q, 1H, J=7.2 Hz), 1.31 (t, 1H, J=7.2 Hz).

Workup

  1. customAn argon degassed
  2. temperaturewas heated in a microwave at 150 degrees for 30 minutes
  3. filtrationwater (2 mL) and the mixture was filtered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel chromatography (EA/DCM=0/100→100/0)
  6. customto give the crude product
  7. customThis material was purified by preparative reverse phase chromatography

Sources & evidence

ORD record
ord-72edce7baf6a48bd965954c5e2843830
Source dataset
uspto-grants-2014_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08796271B2

Reaction notes

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