4-Methoxy-alpha-toluenethiol → HCID 67159624, compound

HRID 1255217Notes

Reaction equation

HRID 1255217 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5](OS(C(F)(F)F)(=O)=O)=[C:6]([C:8]2[N:13]=[C:12]([N:14]3[C:18]([C:19]([F:22])([F:21])[F:20])=[C:17]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH:16]=[N:15]3)[CH:11]=[CH:10][CH:9]=2)[CH:7]=1.[CH3:36][O:37][C:38]1[CH:43]=[CH:42][C:41]([CH2:44][SH:45])=[CH:40][CH:39]=1.CCN(C(C)C)C(C)C.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.CCCCCC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:36][O:37][C:38]1[CH:43]=[CH:42][C:41]([CH2:44][S:45][C:5]2[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][C:6]=2[C:8]2[N:13]=[C:12]([N:14]3[C:18]([C:19]([F:22])([F:21])[F:20])=[C:17]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH:16]=[N:15]3)[CH:11]=[CH:10][CH:9]=2)=[CH:40][CH:39]=1

Participants

8

Reactant 4

HCID 804074-Methoxy-alpha-toluenethiolHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 86633498HCID 86633498, compound

Product 1

HCID 67159624HCID 67159624, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8058HexaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of title compound from Example 243 Step A (2.74 g, 5.23 mmol), 4-methoxy α-toluenethiol (0.88 mL, 6.28 mmol) in 1,4-dioxane (75 mL) were added DIEA (1.83 mL, 10.5 mmol), Xantphos (0.61 g, 1.05 mmol) and tris(dibenzylideneacetone)dipalladium (0) (0.48 g, 0.52 mmol), and the reaction mixture was heated at 90° C. After 15 h, the reaction mixture was allowed to cool to ambient temperature, then was diluted with hexane. The resulting yellow solid was removed by filtration, and the collected organic filtrate was concentrated in vacuo. Purification by flash chromatography on silica gel (5 to 20% ethyl acetate in hexanes) provided the title compound: LCMS m/z 528.6 [M+H]+; 1H NMR (500 MHz, CD2Cl2) δ 8.11 (s, 1H), 7.94 (t, J=7.9 Hz, 1H), 7.72 (d, J=7.8 Hz, 1H), 7.59 (d, J=8.0 Hz, 1H), 7.36 (m, 2 H), 7.17 (d, J=8.0 Hz, 1H), 7.04 (d, J=8.5 Hz, 2H) 6.74 (d, J=8.7 Hz, 2H) 4.35 (q, J=7.1 Hz, 2H), 3.87 (s, 2H), 3.73 (s, 3H), 2.37 (s, 3H), 1.37 (t, J=7.1 Hz, 3H).

Workup

  1. temperatureto cool to ambient temperature
  2. customThe resulting yellow solid was removed by filtration
  3. concentrationthe collected organic filtrate was concentrated in vacuo
  4. customPurification by flash chromatography on silica gel (5 to 20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-333fed8a05fb4e3facabf8a3d623e92f
Source dataset
uspto-grants-2013_06
Patent number
US08455638B2

Reaction notes

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