3-Bromo-5-((triisopropylsilyloxy)methyl)pyridine → 3-Tert-butyl-5-((triisopropylsilyloxy)methyl)pyridine

HRID 2071079노트

반응식

HRID 2071079 반응식
C([Cu])#N.[C:4]([Mg]Br)([CH3:7])([CH3:6])[CH3:5].Br[C:11]1[CH:12]=[N:13][CH:14]=[C:15]([CH2:17][O:18][Si:19]([CH:26]([CH3:28])[CH3:27])([CH:23]([CH3:25])[CH3:24])[CH:20]([CH3:22])[CH3:21])[CH:16]=1>C1COCC1>[C:4]([C:11]1[CH:12]=[N:13][CH:14]=[C:15]([CH2:17][O:18][Si:19]([CH:26]([CH3:28])[CH3:27])([CH:23]([CH3:25])[CH3:24])[CH:20]([CH3:22])[CH3:21])[CH:16]=1)([CH3:7])([CH3:6])[CH3:5]

참가 물질

5

반응물 3

HCID 121095753-Bromo-5-((triisopropylsilyloxy)methyl)pyridineHCID 178418546HCID 178418546, 화합물HCID 178418586HCID 178418586, 화합물

생성물 1

HCID 686715593-Tert-butyl-5-((triisopropylsilyloxy)methyl)pyridine수율 22.9%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-78 °C

실험 절차

A mixture of anhydrous CuCN (3.41 g, 38.03 mmol) in 150 mL of anhydrous THF, and ethereal tert-butylmagnesium bromide (38 mL, 76.1 mmol) was stirred under N2 at −78° C. for 20 min. 3-bromo-5-((triisopropylsilyloxy)methyl)pyridine (3.274 g, 9.51 mmol) in THF was added, and the reaction mixture was stirred for 2-3 h at −78° C. and then overnight at room temperature. The reaction mixture was quenched by dropwise addition of saturated aqueous NH4OH and the pH was adjusted to 10 by using 1 M aqueous NaOH, and the resulting solution was extracted with extracted with EtOAc (3×75 mL). The combined organic extracts were dried (Na2SO4,), and concentrated under vacuum to get a residue which was purified by flash column chromatography to give 3-tert-butyl-5-((triisopropylsilyloxy)methyl)pyridine (0.7 g). 1H NMR shows the products contain the desired product and bromine-removed product. 1H NMR (CDCl3): d: 1.124 (m, 22H), 1.369 (s, 5H), 4.878 (s, 2H), 7.298 (m, 0.5H), 7.738 (m, 1H), 8.414 (s, 0.6H), 8.607 (m, 1.5H).

후처리

  1. stirringthe reaction mixture was stirred for 2-3 h at −78° C.
  2. customovernight
  3. customat room temperature
  4. customThe reaction mixture was quenched by dropwise addition of saturated aqueous NH4OH
  5. extractionthe resulting solution was extracted
  6. extractionwith extracted with EtOAc (3×75 mL)
  7. dry with materialThe combined organic extracts were dried (Na2SO4,)
  8. concentrationconcentrated under vacuum
  9. customto get a residue which
  10. customwas purified by flash column chromatography

출처 및 근거

ORD 기록
ord-909a9e11562b43dc92d7c2a9faba7005
출처 데이터셋
uspto-grants-2012_10
특허 번호
US08299267B2

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