Ethanol → methyl 2-(tert-butoxy)-2-[2-(3,4-dihydro-2H-1-benzopyran-6-yl)-5-phenylthiophen-3-yl]acetate

HRID 590995ノート

反応式

HRID 590995 の反応式
Br[C:2]1[S:3][C:4]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[CH:5][C:6]=1[CH:7]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[C:8]([O:10][CH3:11])=[O:9].CC1(C)C(C)(C)OB([C:31]2[CH:32]=[C:33]3[C:38](=[CH:39][CH:40]=2)[O:37][CH2:36][CH2:35][CH2:34]3)O1.C(=O)([O-])[O-].[Na+].[Na+].C(O)C>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].O>[C:13]([O:12][CH:7]([C:6]1[CH:5]=[C:4]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:3][C:2]=1[C:31]1[CH:40]=[CH:39][C:38]2[O:37][CH2:36][CH2:35][CH2:34][C:33]=2[CH:32]=1)[C:8]([O:10][CH3:11])=[O:9])([CH3:16])([CH3:15])[CH3:14]

参加物

8

反応物 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70819299Methyl 2-(2-bromo-5-phenylthiophen-3-yl)-2-(tert-butoxy)acetate

生成物 1

HCID 70855249methyl 2-(tert-butoxy)-2-[2-(3,4-dihydro-2H-1-benzopyran-6-yl)-5-phenylthiophen-3-yl]acetate収率 70%

試薬・触媒・溶媒 3

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 962Water溶媒2 回HCID 1140Toluene溶媒

反応条件

温度
95 °C

実験手順

A solution of methyl 2-(2-bromo-5-phenylthiophen-3-yl)-2-(tert-butoxy)acetate (11i) (77 mg, 0.20 mmol), 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (94 mg, 0.36 mmol) and sodium carbonate (85 mg, 0.80 mmol) in a mixture of toluene (1.26 mL), ethanol (0.6 mL) and water (0.5 mL) was bubbled with nitrogen for 5 minutes. Palladium tetrakis(triphenylphosphine) (12 mg, 0.01 mmol) was added and the reaction mixture was heated a 95° C. for 4 h. After cooling to room temperature, water (2 mL) was added. The aqueous layer was extracted with toluene (2×8 mL). The organic layers were washed with brine (5 mL), dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 85/15) to provide the desired product (11j) (60 mg, 0.14 mmol, 68%).

後処理

  1. customwas bubbled with nitrogen for 5 minutes
  2. temperatureAfter cooling to room temperature
  3. extractionThe aqueous layer was extracted with toluene (2×8 mL)
  4. washThe organic layers were washed with brine (5 mL)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 85/15)

出典と根拠

ORDレコード
ord-1c16a4ca101442f995469fb7b5201df4
出典データセット
uspto-grants-2016_01
特許番号
US09238026B2

反応ノート

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