Potassium Phosphate, Tribasic → 1,1-Dimethylethyl {[3'-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-(methyloxy)-3-biphenylyl]methyl}carbamate

HRID 564482ノート

反応式

HRID 564482 の反応式
Br[C:2]1[C:3]([O:17][CH3:18])=[C:4]([CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:5]=[CH:6][CH:7]=1.C1(P(C2CCCCC2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2OC)CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[CH3:62][C:63]([Si:66]([CH3:79])([CH3:78])[O:67][CH2:68][C:69]1[CH:70]=[C:71](B(O)O)[CH:72]=[CH:73][CH:74]=1)([CH3:65])[CH3:64]>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:65][C:63]([Si:66]([CH3:79])([CH3:78])[O:67][CH2:68][C:69]1[CH:70]=[C:71]([C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[C:3]=2[O:17][CH3:18])[CH:72]=[CH:73][CH:74]=1)([CH3:62])[CH3:64]

参加物

7

反応物 4

HCID 62657Potassium Phosphate, TribasicHCID 16079156(1R)-Dicyclohexyl(2'-methoxy-[1,1'-binaphthalen]-2-yl)phosphaneHCID 57813344tert-butyl N-[(3-bromo-2-methoxyphenyl)methyl]carbamateHCID 57813382[3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid

生成物 1

HCID 578135081,1-Dimethylethyl {[3'-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-(methyloxy)-3-biphenylyl]methyl}carbamate収率 72%

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
80 °C

実験手順

1,1-Dimethylethyl {[3-bromo-2-(methyloxy)phenyl]methyl}carbamate (5.2 g, 16.4 mmol), Pd(OAc)2 (110.4 mg, 0.49 mmol), dicyclohexyl[2′-(methyloxy)-1,1′-binaphthalen-2-yl]phosphane (317.2 mg, 0.66 mmol) and K3PO4 (4.2 g, 19.7 mmol) were dissolved in dioxane (60 mL). The mixture was heated at 80° C. for 30 min, and then [3-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid (5.2 g, 19.7 mmol) was added. The mixture reaction was stirred at reflux overnight. The solvent was removed under reduced pressure, then diluted with CH2Cl2 (100 mL). The organic layer was washed with water (30 mL), brine (30 mL), and dried over Na2SO4. The product 1,1-dimethylethyl {[3′-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-(methyloxy)-3-biphenylyl]-methyl}carbamate (5.0 g) was purified by flash column chromatography (PE:EA=15:1). (Yield: 72%). 1H NMR (400 MHz, CDCl3): δ 0.11 (s, 6 H), 0.94 (s, 9 H), 1.46 (s, 9 H), 3.37 (s, 3 H), 4.40 (d, J=6 Hz, 2 H), 4.80 (s, 2 H), 5.04 (s, 1 H), 7.12-7.51 (m, 7 H); 13C NMR (100 MHz, CDCl3): δ −5.2, 18.4, 25.9, 28.4, 40.3, 60.4, 65.0, 124.2, 125.0, 126.6, 127.5, 128.3, 128.4, 130.6, 132.3, 134.8, 138.2, 141.5, 155.8; HPLC: retention time: 4.348 min; purity: 99.9%; MS: m/z 453 (M+), 344 (M+−TBS).

後処理

  1. customThe mixture reaction
  2. temperatureat reflux overnight
  3. customThe solvent was removed under reduced pressure
  4. additiondiluted with CH2Cl2 (100 mL)
  5. washThe organic layer was washed with water (30 mL), brine (30 mL)
  6. dry with materialdried over Na2SO4
  7. customThe product 1,1-dimethylethyl {[3′-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)-2-(methyloxy)-3-biphenylyl]-methyl}carbamate (5.0 g) was purified by flash column chromatography (PE:EA=15:1)

出典と根拠

ORDレコード
ord-4bc5530b6f434777a9343a750e1644bb
出典データセット
uspto-grants-2011_11
特許番号
US08067408B2

反応ノート

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