Dichloromethane → HCID 117733756, compound

HRID 1772739Notes

Reaction equation

HRID 1772739 reaction equation
Cl[C:2]1[C:3]2[N:4]([CH:27]=[C:28]([CH2:30][OH:31])[N:29]=2)[C:5]([C:8]2[CH:9]=[CH:10][C:11]([N:14]3[CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]3)=[N:12][CH:13]=2)=[CH:6][N:7]=1.CC1(C)C(C)(C)OB([C:40]2[CH:45]=[CH:44][N:43]=[CH:42][CH:41]=2)O1.C([O-])([O-])=O.[Cs+].[Cs+].C(Cl)Cl>O1CCOCC1.CCOC(C)=O.O>[OH:31][CH2:30][C:28]1[N:29]=[C:3]2[C:2]([C:40]3[CH:45]=[CH:44][N:43]=[CH:42][CH:41]=3)=[N:7][CH:6]=[C:5]([C:8]3[CH:9]=[CH:10][C:11]([N:14]4[CH2:15][CH2:16][N:17]([C:20]([O:22][C:23]([CH3:25])([CH3:24])[CH3:26])=[O:21])[CH2:18][CH2:19]4)=[N:12][CH:13]=3)[N:4]2[CH:27]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 10796Cesium carbonateHCID 27346484-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridineHCID 117733767HCID 117733767, compound

Product 1

HCID 117733756HCID 117733756, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

To a mixture of compound 87c (95.0 mg, 0.214 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (48.2 mg, 0.235 mmol), Cs2CO3 (174 mg, 0.534 mmol), and Pd(dppf)2.CH2Cl2 (17.5 mg, 0.0214 mmol) in 1,4-dioxane (3 mL) was added 1.5 mL of water. The resulting mixture was stirred at 90° C. for 4 h. After cooling to rt, the mixture was treated with EtOAc (30 mL) and washed with H2O (2×10 mL) and brine (10 mL). Removal of the solvent gave a residue, which was purified by flash column chromatography on silica gel (0-6% MeOH/DCM) to give compound 87d as a bright yellow-green solid. 1H-NMR (CDCl3; 400 MHz) δ 8.84 (br. s., 2H), 8.65 (d, J=4.9 Hz, 2H), 8.51 (s, 1H), 7.97 (s, 1H), 7.87 (s, 1H), 7.82 (d, J=8.8 Hz, 1H), 6.82 (d, J=8.8 Hz, 1H), 4.96 (s, 2H), 3.66-3.75 (m, 4H), 3.55-3.66 (m, 4H), 3.00 (br. s., 1H), 1.51 (s, 9H). Mass spectrum (LCMS, ESI pos.): Calcd. for C26H29N2O3, 488.2 (M+H). found 488.2.

Workup

  1. temperatureAfter cooling to rt
  2. washwashed with H2O (2×10 mL) and brine (10 mL)
  3. customRemoval of the solvent
  4. customgave a residue, which
  5. customwas purified by flash column chromatography on silica gel (0-6% MeOH/DCM)

Sources & evidence

ORD record
ord-d0b52e6976bd46848cdc8078c7c559fe
Source dataset
uspto-grants-2016_02
Patent number
US09249163B2

Reaction notes

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