Water → HCID 57585828、化合物

HRID 547660ノート

反応式

HRID 547660 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[CH2:7][CH:6]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:5]2.O.[CH3:20][N:21](C)C=O>C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2].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].[C-]#N.[Zn+2].[C-]#N>[C:20]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[CH2:7][CH:6]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:5]2)#[N:21]

参加物

7

反応物 3

HCID 962WaterHCID 6228DimethylformamideHCID 57585894tert-Butyl N-(5-bromo-2,3-dihydro-1H-inden-2-yl)carbamate

生成物 1

HCID 57585828HCID 57585828、化合物収率 78%

試薬・触媒・溶媒 3

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 15826098Cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(diphenyl)phosphane;iron(2+)触媒

反応条件

温度
110 °C

実験手順

A flask containing 1,1-dimethylethyl (5-bromo-2,3-dihydro-1H-inden-2-yl)carbamate (3.0 g, 9.26 mmol) from the preceding step, diphenylphosphinoferrocene (645 mg, 1.16 mmol), Pd2 dba3 (532 mg, 0.58 mmol), zinc cyanide (1.50 g, 12.8 mmol) and water in 50 mL dimethylformamide was degassed four times under nitrogen and allowed to stir at 110° C. for 21 hours. Upon cooling the reaction was quenched with saturated NH4Cl and the organics were taken up in ethyl acetate. The organic layer was washed with water (3×), sat. NaCl and dried over MgSO4. The solvent was removed in vacuo and the residual orange-yellow oil was purified by silica gel column chromatography (15-40% ethyl acetate/hexanes) yielding 1.85 g (7.18 mmol, 78% yield) of the 1,1-dimethylethyl (5-cyano-2,3-dihydro-1H-inden-2-yl)carbamate as an off-white solid. 1H NMR (400 MHz, CDCl3) delta 7.47 (s, 1H), 7.45 (d, 1H, J=7.9 Hz), 7.28 (d, 1H, J=7.7 Hz), 4.69 (br.s), 1H), 4.47 (s(br), 1H), 3.33-3.25 (m, 2H), 2.86-2.80 (m, 2H), 2.79 (s, 9H) ppm. (M+1) 259.1, 2.46 min (LC/MS method A).

後処理

  1. customwas degassed four times under nitrogen
  2. temperatureUpon cooling the reaction
  3. customwas quenched with saturated NH4Cl
  4. washThe organic layer was washed with water (3×), sat. NaCl
  5. dry with materialdried over MgSO4
  6. customThe solvent was removed in vacuo
  7. customthe residual orange-yellow oil was purified by silica gel column chromatography (15-40% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-4054291e337f4baba72c0123be33ba33
出典データセット
uspto-grants-2011_05
特許番号
US07939528B2

反応ノート

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