Dimethyl Sulfoxide → HCID 69969629, compound

HRID 842019Notes

Reaction equation

HRID 842019 reaction equation
[C:1]([O:5][C:6]([N:8]([CH:36]1[CH2:41][CH2:40][O:39][CH2:38][CH2:37]1)[CH2:9][CH2:10][NH:11][C:12]1[N:17]2[N:18]=[C:19]([CH3:34])[C:20]([C:21]3[C:26]([Cl:27])=[CH:25][C:24](OS(C)(=O)=O)=[CH:23][C:22]=3[Cl:33])=[C:16]2[N:15]=[C:14]([CH3:35])[CH:13]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.CS(C)=O>CO.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:1][O:5][C:6](=[O:7])[C:24]1[CH:23]=[C:22]([Cl:33])[C:21]([C:20]2[C:19]([CH3:34])=[N:18][N:17]3[C:12]([NH:11][CH2:10][CH2:9][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[CH:36]4[CH2:41][CH2:40][O:39][CH2:38][CH2:37]4)=[CH:13][C:14]([CH3:35])=[N:15][C:16]=23)=[C:26]([Cl:27])[CH:25]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 88078764HCID 88078764, compound

Product 1

HCID 69969629HCID 69969629, compoundYield 176.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolvent

Conditions

Temperature
70 °C

Procedure

A suspension of methanesulfonic acid 4-(7-{2-[tert-butoxycarbonyl-(tetrahydro-pyran-4-yl)-amino]-ethylamino}-2,5-dimethyl-pyrazolo[1,5-a]pyrimidin-3-yl)-3,5-dichloro-phenyl ester (188 mg, 0.276 mmol) from Example 134, step B, 1,3-bis(diphenylphosphino)propane (30 mg 0.073 mmol), triethylamine (0.10 mL), and palladium(II) acetate (25 mg, 0.11 mmol) in methanol (3.5 mL)/dimethylsulfoxide (3.5 mL) was degassed with a stream of carbon monoxide and then shaken for 4 hours at 70° C. under 40 psi carbon monoxide. The mixture was filtered through Celite, diluted with ethyl acetate and washed with water, dried (Na2SO4), concentrated under reduced pressure, and chromatographed (3:1 to 1:1 hexanes/ethyl acetate) to afford the product (144 mg, 88%): +APcI MS (M+1)+592; 1H NMR (CDCl3) δ: 8.04 (s, 2H), 5.83 (br s, 1H), 3.92 (s, 3H), 2.43 (s, 3H), 2.24 (s, 3H), 1.53 (s, 9H).

Workup

  1. customwas degassed with a stream of carbon monoxide
  2. filtrationThe mixture was filtered through Celite
  3. additiondiluted with ethyl acetate
  4. washwashed with water
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure
  7. customchromatographed (3:1 to 1:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-6de882e3f58b4a55a91cba91ad998827
Source dataset
uspto-grants-2002_04
Patent number
US06372743B1

Reaction notes

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