2-Bromo-N-(tert-butoxycarbonyl)benzylamine → 2'-[(t-Butoxycarbonylamino)methyl]-4-[(t-butyldimethylsiloxy)-methyl]-1,1'-biphenyl

HRID 1080743ノート

反応式

HRID 1080743 の反応式
[O:1]([CH2:9][C:10]1[CH:15]=[CH:14][C:13](B(O)O)=[CH:12][CH:11]=1)[Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3].O.O.O.O.O.O.[OH-].[Ba+2].[OH-].[C:28]([O:32][C:33]([NH:35][CH2:36][C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=1Br)=[O:34])([CH3:31])([CH3:30])[CH3:29]>COCCOC.[Cl-].[NH4+].[Pd].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>[C:28]([O:32][C:33]([NH:35][CH2:36][C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=1[C:13]1[CH:14]=[CH:15][C:10]([CH2:9][O:1][Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3])=[CH:11][CH:12]=1)=[O:34])([CH3:31])([CH3:29])[CH3:30]

参加物

7

反応物 3

HCID 70183002-Bromo-N-(tert-butoxycarbonyl)benzylamineHCID 233654354-(tert-Butyldimethylsilyloxymethyl)phenylboronic acidHCID 129776469Barium(2+);dihydroxide;hexahydrate

生成物 1

HCID 233654482'-[(t-Butoxycarbonylamino)methyl]-4-[(t-butyldimethylsiloxy)-methyl]-1,1'-biphenyl収率 75.1%

試薬・触媒・溶媒 3

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 80711,2-Dimethoxyethane溶媒HCID 25517Ammonium Chloride溶媒

反応条件

温度
80 °C

実験手順

To a solution of 1.0 g (3.8 mmol) of 4-(t-butyldimethaylsilyoxymethyl)phenylboronic acid (Step E) in 24 mL of 1,2-dimethyoxyethane was added 4 mL of water,m 1.02 g (5.37 mmol) of barium hydroxide hexahydrate, 1.02 g (3.58 mmol) of N-(t-butoxycarbonyl)-2-bromobenzylamine (Step F) and 206 mg (0.18 mmol) of tetrakis(triphenylphosphine) palladium. The resulting mixture was heated under nitrogen at 80° C. for 2.5 hours then cooled to room temperature. The reaction mixture was diluted with 40 mL of saturated aqueous ammonium chloride. The solution was transferred to a separatory funnel and extracted with ether (3×75 mL). The combined ether extracts were washed with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride, dried over magnesium sulfate and then filtered. The solvent was removed under vacuum to give a crude product which was purified by column chromatography on silica gel eluting with hexanes/ethyl acetate (85:15) to afford 1.15 g (75%) of the product as a clear oil. FAB-MS: calculated for C25H37NO3Si 427; found 314. 1H NMR (200 MHz, CDCl3): 0.10 (s, 6H), 0.92 (s, 9H), 1.40 (s, 9H), 4.27 (d, 5 Hz, 2H), 4.60 (s, 1H), 4.78 (s, 2H), 7.18-7.45 (m, 8H).

後処理

  1. temperaturethen cooled to room temperature
  2. customThe solution was transferred to a separatory funnel
  3. extractionextracted with ether (3×75 mL)
  4. washThe combined ether extracts were washed with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customThe solvent was removed under vacuum
  8. customto give a crude product which
  9. customwas purified by column chromatography on silica gel eluting with hexanes/ethyl acetate (85:15)

出典と根拠

ORDレコード
ord-09a9b8dc0e6b45d6a534e1bf219e9130
出典データセット
uspto-grants-1996_12
特許番号
US05583130

反応ノート

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