Cesium carbonate → HCID 90332468, compound

HRID 595573Notes

Reaction equation

[Br:1][C:2]1[C:3]([N:16]([CH3:21])[S:17]([CH3:20])(=[O:19])=[O:18])=[CH:4][C:5]2[O:9][C:8](I)=[C:7]([C:11]([NH:13][CH3:14])=[O:12])[C:6]=2[CH:15]=1.[S:22]1[CH2:27][CH:26]=[C:25](B2OC(C)(C)C(C)(C)O2)[CH2:24][CH2:23]1.C([O-])([O-])=O.[Cs+].[Cs+].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Br:1][C:2]1[C:3]([N:16]([CH3:21])[S:17]([CH3:20])(=[O:19])=[O:18])=[CH:4][C:5]2[O:9][C:8]([C:25]3[CH2:26][CH2:27][S:22][CH2:23][CH:24]=3)=[C:7]([C:11]([NH:13][CH3:14])=[O:12])[C:6]=2[CH:15]=1

Participants

Conditions

Temperature: 100 °C

Procedure

To a solution of 5-bromo-2-iodo-N-methyl-6-(N-methylmethylsulfonamido)benzofuran-3-carboxamide (800 mg, 1.6 mmol), 2-(3,6-dihydro-2H-thiopyran-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (371 mg, 1.6 mmol) and Cs2CO3 (1.07 g, 3.28 mmol) in 1,4-dioxane (20 mL) was added Pd(dppf)Cl2 (50 mg) and tri-o-tolylphosphine (50 mg) under nitrogen. The reaction mixture was heated at 100° C. for 4 h, concentrated in vacuo to remove 1,4-dioxane and purified by column chromatography (PE:EA=3:1) to give the compound 5-bromo-2-(3,6-dihydro-2H-thiopyran-4-yl)-N-methyl-6-(N-methylmethylsulfonamido)benzofuran-3-carboxamide (250 mg, yield: 33%). 1H-NMR (CDCl3, 400 MHz) δ 8.09 (s, 1H), 7.59 (s, 1H), 6.73 (s, 1H), 6.06 (brs, 1H), 3.38 (t, J=2.0 Hz, 2H), 3.30 (s, 3H), 3.05 (s, 3H), 3.00 (d, J=4.8 Hz, 3H), 2.87 (t, J=5.6 Hz, 2H), 2.70˜2.76 (m, 2H). MS (M+H)+: 459/461.

Workup

concentrationconcentrated in vacuo
customto remove 1,4-dioxane
custompurified by column chromatography (PE:EA=3:1)

Sources & evidence

ORD record: ord-a5ce715bfb334bf9908be98b3dadaca5
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09242998B2

Reaction notes

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