Benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylate → Benzyl 3-(diethoxyphosphorylamino)-4-methylpiperidine-1-carboxylate

HRID 73559노트

반응식

HRID 73559 반응식
[CH3:1][Mg]Br.[CH2:4]([O:6][P:7]([N:12]1[CH:18]2[CH:13]1[CH2:14][CH2:15][N:16]([C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20])[CH2:17]2)([O:9][CH2:10][CH3:11])=[O:8])[CH3:5]>C1COCC1.[Cu]I>[CH2:4]([O:6][P:7]([NH:12][CH:18]1[CH:13]([CH3:1])[CH2:14][CH2:15][N:16]([C:19]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[O:20])[CH2:17]1)([O:9][CH2:10][CH3:11])=[O:8])[CH3:5]

참가 물질

5

반응물 2

HCID 59455678Benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylateHCID 178418573HCID 178418573, 화합물

생성물 1

HCID 60205257Benzyl 3-(diethoxyphosphorylamino)-4-methylpiperidine-1-carboxylate수율 35%

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
10 °C

실험 절차

To a suspension of CuI (0.3 equiv.) in anhydrous THF (0.1M) was added methyl magnesium bromide (3M solution in Et2O, 10 equiv.) at −40° C. The reaction was stirred for 30 min, followed by addition of benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylate (1.0 equiv.) in THF (0.1M) at −40° C. Allowed the reaction to warm to 10° C. over 5 h, then quenched with water and extracted with ethyl acetate. The organic phase was concentrated under vacuo and purified via silica gel column chromatography eluting with ethyl acetate and hexanes (50% to 100% ethyl acetate) to yield benzyl 3-(diethoxyphosphorylamino)-4-methylpiperidine-1-carboxylate in 35% yield. LCMS (m/z): 385.0 (MH+), Rt=3.38 min.

후처리

  1. customAllowed the reaction
  2. customquenched with water
  3. extractionextracted with ethyl acetate
  4. concentrationThe organic phase was concentrated under vacuo
  5. custompurified via silica gel column chromatography
  6. washeluting with ethyl acetate and hexanes (50% to 100% ethyl acetate)

출처 및 근거

ORD 기록
ord-0db8e0a420254cecb1c79e6ff76e14c6
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08829193B2

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