Tributylstannane → HCID 86700265, compound

HRID 879456Notes

Reaction equation

HRID 879456 reaction equation
[CH3:1][N:2]1[C:6]2=[CH:7][N:8]=[C:9]([Sn](CCCC)(CCCC)CCCC)[CH:10]=[C:5]2[C:4]([CH3:24])=[N:3]1.[C:25]([O:29][C@@H:30]([C:36]1[C:51]([CH3:52])=[CH:50][C:39]2[N:40]=[C:41]([C:43]3[CH:48]=[CH:47][N:46]=[C:45](Cl)[CH:44]=3)[S:42][C:38]=2[C:37]=1[C:53]1[CH:58]=[CH:57][C:56]([Cl:59])=[CH:55][CH:54]=1)[C:31]([O:33][CH2:34][CH3:35])=[O:32])([CH3:28])([CH3:27])[CH3:26].[Cl-].[Li+].C([SnH](CCCC)CCCC)CCC>O1CCOCC1.ClCCl.[Cu]I.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.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:25]([O:29][C@@H:30]([C:36]1[C:51]([CH3:52])=[CH:50][C:39]2[N:40]=[C:41]([C:43]3[CH:48]=[CH:47][N:46]=[C:45]([C:9]4[CH:10]=[C:5]5[C:4]([CH3:24])=[N:3][N:2]([CH3:1])[C:6]5=[CH:7][N:8]=4)[CH:44]=3)[S:42][C:38]=2[C:37]=1[C:53]1[CH:54]=[CH:55][C:56]([Cl:59])=[CH:57][CH:58]=1)[C:31]([O:33][CH2:34][CH3:35])=[O:32])([CH3:26])([CH3:27])[CH3:28]

Participants

10

Reactant 4

HCID 5948TributylstannaneHCID 433294Lithium ChlorideHCID 86700142(S)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(2-chloropyridin-4-yl)-5-methylbenzo[d]thiazol-6-yl)acetateHCID 86700266HCID 86700266, compound

Product 1

HCID 86700265HCID 86700265, compound

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 1,3-dimethyl-5-(tributylstannyl)-1H-pyrazolo[3,4-c]pyridine (31 mg, 0.071 mmol), (S)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(2-chloropyridin-4-yl)-5-methylbenzo[d]thiazol-6-yl)acetate (30.1 mg, 0.057 mmol), copper(I) iodide (13.5 mg, 0.071 mmol) and lithium chloride (15.1 mg, 0.355 mmol) in dioxane (0.5 mL) was sparged with nitrogen for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (8.9 mg, 0.0008 mmol) and trans-dichlorobis(triphenylphosphine)palladium (II) (5.2 mg, 0.007 mmol) were added and reaction mixture was heated at 120° C. for 5 hours. Reaction mixture was cooled to rt, diluted with dichloromethane, adsorbed onto silica gel and purified by CombiFlash (0 to 70% EtOAc/Hex) to give product contaminated with tributylstannane impurity. LCMS-ESI+: calc'd for C35H35ClN5O3S: 640.2 (M+H+); Found: 640.4 (M+H+).

Workup

  1. customwas sparged with nitrogen for 10 minutes
  2. customreaction mixture
  3. customReaction mixture
  4. temperaturewas cooled to rt
  5. custompurified by CombiFlash (0 to 70% EtOAc/Hex)
  6. customto give product

Sources & evidence

ORD record
ord-6c89cdcf241142d0b86b35b73711153d
Source dataset
uspto-grants-2015_03
Patent number
US08987250B2

Reaction notes

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