Hexane → Tert-butyl{[3-(methylsulfinyl)-3-(methylthio)cyclobutyl]oxy}diphenylsilane

HRID 1426280노트

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HRID 1426280 반응식
[CH3:1][S:2]([CH2:4][S:5][CH3:6])=[O:3].C([Li])CCC.CCCCCC.Br[CH2:19][CH:20]([CH2:39]Br)[O:21][Si:22]([C:35]([CH3:38])([CH3:37])[CH3:36])([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1>O1CCCC1.O>[C:35]([Si:22]([O:21][CH:20]1[CH2:39][C:4]([S:2]([CH3:1])=[O:3])([S:5][CH3:6])[CH2:19]1)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([CH3:38])([CH3:37])[CH3:36]

참가 물질

7

반응물 4

HCID 8058HexaneHCID 99129Methyl (methylsulfinyl)methyl sulfideHCID 69673452[2-Bromo-1-(bromomethyl)ethoxy](tert-butyl)diphenylsilaneHCID 178418339Butyllithium

생성물 1

HCID 86666495Tert-butyl{[3-(methylsulfinyl)-3-(methylthio)cyclobutyl]oxy}diphenylsilane

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

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온도
-10 °C

실험 절차

To a solution of (methylsulfinyl)(methylthio)methane (27.70 g, 223.0 mmol) in tetrahydrofuran (90 mL) at −10° C. was added dropwise, a solution of 2.5M n-butyllithium in hexane (89.2 mL, 223 mmol). The mixture was stirred at −10° C. for 2 hours. It was then cooled to −78° C. and transferred by cannula in a slow manner to a solution of [2-bromo-1-(bromomethyl)ethoxy](tert-butyl)diphenylsilane (42 g, 93 mmol, from Step 1) in tetrahydrofuran (70 mL, 900 mmol) held at −78° C. The mixture was stirred with warming to room temperature over 2 nights. Water was added, and then the product was extracted with three portions of DCM. The combined extracts were dried over sodium sulfate, filtered and concentrated. Flash chromatography (eluting with a gradient from 0-100% ethyl acetate/hexanes) afforded desired product as a mixture of diastereomers (34.1 g, 88%). 1H NMR (300 MHz, CDCl3), diastereomers: δ 7.74-7.58 (m, 8H), 7.48-7.31 (m, 10H), 4.52 (tt, 1H), 4.42 (tt, 1H), 3.05-1.99 (m, 8H), 2.47 (s, 3H), 2.42 (s, 3H), 2.13 (s, 3H), 2.00 (s, 3H), 1.05 (s, 9H), 1.02 (s, 9H).

후처리

  1. temperatureIt was then cooled to −78° C.
  2. customheld at −78° C
  3. stirringThe mixture was stirred
  4. temperaturewith warming to room temperature over 2 nights
  5. extractionthe product was extracted with three portions of DCM
  6. dry with materialThe combined extracts were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. washFlash chromatography (eluting with a gradient from 0-100% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-bd4d1bfdab43467889798dd0451d6668
출처 데이터셋
uspto-grants-2015_01
특허 번호
US08933085B2

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