Chlorotrimethylsilane → tert-Butyl3-(2-{[tert-butyl(dimethyl)silyl]oxy)-5-chlorophenyl)azetidine-1-carboxylate

HRID 46312

反応式

HRID 46312 の反応式
BrCCBr.Cl[Si](C)(C)C.I[CH:11]1[CH2:14][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12]1.[C:22]([Si:26]([O:29][C:30]1[CH:35]=[CH:34][C:33]([Cl:36])=[CH:32][C:31]=1I)([CH3:28])[CH3:27])([CH3:25])([CH3:24])[CH3:23].O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>CN(C)C=O.[Zn].C1(/C=C/C(=O)/C=C/C2C=CC=CC=2)C=CC=CC=1.[Pd]>[Si:26]([O:29][C:30]1[CH:35]=[CH:34][C:33]([Cl:36])=[CH:32][C:31]=1[CH:11]1[CH2:14][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12]1)([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:28])[CH3:27]

参加物

9

反応物 5

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 521585Tris(furan-2-yl)phosphaneHCID 11000522Tert-butyl 3-iodoazetidine-1-carboxylateHCID 59436493Tert-butyl(4-chloro-2-iodophenoxy)dimethylsilane

生成物 1

HCID 59436503tert-Butyl3-(2-{[tert-butyl(dimethyl)silyl]oxy)-5-chlorophenyl)azetidine-1-carboxylate

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 15673654(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one palladium触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
60 °C

実験手順

Zinc powder (700 mg, 10.7 mmol) was suspended in N,N-dimethylformamide (20 ml) under nitrogen. 1,2-dibromoethane (120 ul) was added and suspension heated to 60° C. for 10 minutes before cooling to room temperature. Chlorotrimethylsilane (180 ul) was added and the mixture heated to 60° C. for 10 minutes then cooled to room temperature. tert-Butyl 3-iodoazetidine-1-carboxylate (3.0 g, 10.6 mmol) was added with a slight exotherm observed. The mixture was stirred at room temperature for 1 hour before the addition of tert-butyl(4-chloro-2-iodophenoxy)dimethylsilane (Preparation 239, 2.2 g, 5.97 mmol) followed immediately by tri-2-furylphosphine (250 mg, 1.08 mmol) and (1E,4E)-1,5-diphenylpenta-1,4-dien-3-one-palladium (2:1) (300 mg, 0.52 mmol). The mixture was stirred at room temperature for 30 minutes then heated at 70° C. for 5 hours before concentration in vacuo. The residue was partitioned between ethyl acetate (100 ml) and aqueous sodium carbonate solution (50 ml). The organic extract was dried over sodium sulphate, filtered and evaporated in vacuo to afford the title compound as a brown oil, 3.2 g,

後処理

  1. temperaturebefore cooling to room temperature
  2. temperaturethe mixture heated to 60° C. for 10 minutes
  3. temperaturethen cooled to room temperature
  4. temperaturethen heated at 70° C. for 5 hours before concentration in vacuo
  5. customThe residue was partitioned between ethyl acetate (100 ml) and aqueous sodium carbonate solution (50 ml)
  6. extractionThe organic extract
  7. dry with materialwas dried over sodium sulphate
  8. filtrationfiltered
  9. customevaporated in vacuo

出典と根拠

ORDレコード
ord-44909872de054f04a9baddf64ddcecc0
出典データセット
uspto-grants-2013_09
特許番号
US08541588B2

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