Lithium Chloride → (S)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(1,2-dimethyl-3-oxo-2,3-dihydro-1H-indazol-6-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

HRID 879380ノート

反応式

HRID 879380 の反応式
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:24][C:25]([CH3:28])([CH3:27])[CH3:26])[C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:8]([CH3:29])=[CH:7][C:5]=2[N:6]=1.[CH3:30][N:31]1[C:39]2[C:34](=[CH:35][CH:36]=[C:37]([Sn](CCCC)(CCCC)CCCC)[CH:38]=2)[C:33](=[O:53])[N:32]1[CH3:54].[Li+].[Cl-]>O1CCOCC1.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.[Cu]I>[C:25]([O:24][C@@H:18]([C:9]1[C:8]([CH3:29])=[CH:7][C:5]2[N:6]=[C:2]([C:37]3[CH:38]=[C:39]4[C:34]([C:33](=[O:53])[N:32]([CH3:54])[N:31]4[CH3:30])=[CH:35][CH:36]=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][CH2:22][CH3:23])=[O:20])([CH3:28])([CH3:27])[CH3:26]

参加物

7

反応物 3

HCID 433294Lithium ChlorideHCID 86700141(S)-ethyl 2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyacetateHCID 867001751,2-dimethyl-6-(tributylstannyl)-1H-indazol-3(2H)-one

生成物 1

HCID 86700190(S)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(1,2-dimethyl-3-oxo-2,3-dihydro-1H-indazol-6-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

To a solution of (S)-ethyl 2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyacetate (30.0 mg, 0.060 mmol) and 1,2-dimethyl-6-(tributylstannyl)-1H-indazol-3(2H)-one (32.5 mg, 0.072 mmol) in dioxane (0.7 mL) was added Pd(PPh3)4 (7.0 mg, 0.006 mmol), CuI (4.0 mg, 0.018 mmol) and LiCl (8.0 mg, 0.182 mmol). The reaction was degassed for 5 minutes with N2 and then heated at 100° C. for 7 h. After cooling, the reaction mixture was diluted with EtOAc, extracted with H2O, brine, dried over Na2SO4, filtered and concentrated and purified by flash column chromatography (silica gel, 0 to 100% ethyl acetate/hexanes) to give the desired product. LCMS-ESI+ (m/z): [M+H]+ calcd for C31H33ClN3O4S: 578.2; found: 578.3.

後処理

  1. customThe reaction was degassed for 5 minutes with N2
  2. temperatureAfter cooling
  3. additionthe reaction mixture was diluted with EtOAc
  4. extractionextracted with H2O, brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by flash column chromatography (silica gel, 0 to 100% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-3bcacc4167bd4dbe8f7b60bafc1b4e96
出典データセット
uspto-grants-2015_03
特許番号
US08987250B2

反応ノート

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