Methyl (S)-2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-(tert-butoxy)acetate → (S)-methyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(1,3-dimethyl-1H-pyrazolo[4,3-d]pyrimidin-5-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

HRID 879639Notes

Reaction equation

HRID 879639 reaction equation
Br[C:2]1[S:3][C:4]2[C:10]([C:11]3[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=3)=[C:9]([C@H:18]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[C:19]([O:21][CH3:22])=[O:20])[C:8]([CH3:28])=[CH:7][C:5]=2[N:6]=1.[CH3:29][N:30]1[C:38]2[CH:37]=[N:36][C:35]([Sn](CCCC)(CCCC)CCCC)=[N:34][C:33]=2[C:32]([CH3:52])=[N:31]1>O1CCOCC1.[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>[C:24]([O:23][C@@H:18]([C:9]1[C:8]([CH3:28])=[CH:7][C:5]2[N:6]=[C:2]([C:35]3[N:36]=[CH:37][C:38]4[N:30]([CH3:29])[N:31]=[C:32]([CH3:52])[C:33]=4[N:34]=3)[S:3][C:4]=2[C:10]=1[C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=1)[C:19]([O:21][CH3:22])=[O:20])([CH3:27])([CH3:26])[CH3:25]

Participants

6

Reactant 2

HCID 86699809Methyl (S)-2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-(tert-butoxy)acetateHCID 867004481,3-dimethyl-5-(tributylstannyl)-1H-pyrazolo[4,3-d]pyrimidine

Product 1

HCID 86700447(S)-methyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(1,3-dimethyl-1H-pyrazolo[4,3-d]pyrimidin-5-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

Reagents, catalysts & solvents 3

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

Conditions

Temperature
90 °C

Procedure

A mixture of (S)-methyl 2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyacetate (0.055 g, 0.107 mmol), 1,3-dimethyl-5-(tributylstannyl)-1H-pyrazolo[4,3-d]pyrimidine (0.058 mg, 0.133 mmol), copper(I) iodide (6 mg, 0.032 mmol) and tetrakis(triphenylphosphine)palladium(0) (11 mg, 0.012 mmol) in dioxane (1 mL) was heated at 90° C. for 16 hr. Reaction mixture was cooled to rt, filtered through a syringe filter and purified by CombiFlash (0 to 70% EtOAc/Hex) to give title product. LCMS-ESI+: calc'd for C28H29ClN5O3S: 550.2 (M+H+); Found: 550.3 (M+H+); 1H NMR (400 MHz, Methanol-d4) δ 9.32 (s, 1H), 7.88 (s, 1H), 7.70-7.53 (m, 4H), 5.30 (s, 1H), 4.13 (s, 3H), 3.75 (s, 3H), 2.57 (s, 3H), 2.54 (s, 3H), 0.97 (s, 9H).

Workup

  1. customReaction mixture
  2. temperaturewas cooled to rt
  3. filtrationfiltered through a syringe
  4. filtrationfilter
  5. custompurified by CombiFlash (0 to 70% EtOAc/Hex)

Sources & evidence

ORD record
ord-86794df3b5b64a6aadbe128155a1f56f
Source dataset
uspto-grants-2015_03
Patent number
US08987250B2

Reaction notes

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