4,4,5,5-Tetramethyl[1,3,2]dioxaborolane → 2-(2-(Butyloxy)-5-(methyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

HRID 2101748ノート

反応式

HRID 2101748 の反応式
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[CH:4][C:3]=1[O:10][CH2:11][CH2:12][CH2:13][CH3:14].O(C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1)C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:54][C:55]1([CH3:62])[C:59]([CH3:61])([CH3:60])[O:58][BH:57][O:56]1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:11]([O:10][C:3]1[CH:4]=[CH:5][C:6]([O:8][CH3:9])=[CH:7][C:2]=1[B:57]1[O:58][C:59]([CH3:61])([CH3:60])[C:55]([CH3:62])([CH3:54])[O:56]1)[CH2:12][CH2:13][CH3:14]

参加物

6

反応物 3

HCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 578018162-Bromo-1-butoxy-4-methoxybenzene

生成物 1

HCID 576724442-(2-(Butyloxy)-5-(methyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane収率 41%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
95 °C

実験手順

A mixture of 2-bromo-1-butoxy-4-methoxybenzene (1.2 g, 4.7 mmol), TEA (2.6 mL, 19 mmol), (oxydi-2,1-phenylene)bis(diphenylphosphine) (0.51 g, 0.95 mmol) (Aldrich, CAS# 166330-10-5), palladium(II) acetate (0.11 g, 0.47 mmol), and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.1 mL, 14 mmol) (Aldrich, CAS# 25015-63-8) in 1,4-dioxane (5.0 mL) was stirred overnight at 95° C. The mixture was cooled to room temperature, quenched with saturated aqueous ammonium chloride, and extracted with ether. The combined organic layers were dried over MgSO4 and concentrated. The crude product was purified by silica gel flash chromatography (0-10% EtOAc/hexane) to afford compound C.3 (0.60 g, 41% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.16 (d, J=3.1 Hz, 1H), 6.91 (dd, J=3.1, 9.0 Hz, 1H), 6.79 (d, J=9.0 Hz, 1H), 3.91 (t, J=6.3 Hz, 2H), 3.78 (s, 3H), 1.75 (m, 2H), 1.54 (m, 2H), 1.34 (s, 12H), 0.96 (t, J=7.4, 3H).

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. customquenched with saturated aqueous ammonium chloride
  3. extractionextracted with ether
  4. dry with materialThe combined organic layers were dried over MgSO4
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel flash chromatography (0-10% EtOAc/hexane)
  7. customto afford compound C.3 (0.60 g, 41% yield) as a colorless oil

出典と根拠

ORDレコード
ord-e64b106892d4477aba7d7786c397c676
出典データセット
uspto-grants-2009_08
特許番号
US07572934B2

反応ノート

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