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

HRID 46312

반응식

HRID 46312 반응식
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]

참가 물질

9

반응물 5

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

생성물 1

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

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 15673654(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one palladium촉매HCID 6228Dimethylformamide용매

반응 조건

온도
60 °C

실험 절차

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,

후처리

  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

출처 및 근거

ORD 기록
ord-44909872de054f04a9baddf64ddcecc0
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08541588B2

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