N-(Diphenylmethylene)glycine tert-butyl ester → tert-butyl 3-(1-benzyl-3-nitro-1H-pyrazol-4-yl)-N-(diphenylmethylene)-L-alaninate

HRID 1426272

반응식

HRID 1426272 반응식
[C:1]1([C:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[N:8][CH2:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:23]([N:30]1[CH:34]=[C:33]([CH2:35]Br)[C:32]([N+:37]([O-:39])=[O:38])=[N:31]1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C=CCO[C@H](C1C2C(=CC=CC=2)N=CC=1)[C@H]1[N+]2(CC3C4C(=CC=CC=4)C=C4C=3C=CC=C4)C[C@H](C=C)[C@@H](CC2)C1.[Br-].O.[OH-].[Cs+]>ClCCl>[CH2:23]([N:30]1[CH:34]=[C:33]([CH2:35][C@@H:9]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[N:8]=[C:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C:32]([N+:37]([O-:39])=[O:38])=[N:31]1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

참가 물질

6

반응물 4

HCID 688171N-(Diphenylmethylene)glycine tert-butyl esterHCID 10886583O-Allyl-N-(9-anthracenylmethyl)cinchonidinium bromideHCID 23679066Caesium hydroxide--water (1/1/1)HCID 679630121-benzyl-4-(bromomethyl)-3-nitro-1H-pyrazole

생성물 1

HCID 86674197tert-butyl 3-(1-benzyl-3-nitro-1H-pyrazol-4-yl)-N-(diphenylmethylene)-L-alaninate

시약·촉매·용매 1

HCID 6344Dichloromethane용매

반응 조건

온도
-30 °C

실험 절차

To a −30° C. solution of tert-butyl N-(diphenylmethylene)glycinate (98% 1.16 g, 3.85 mmol), C4 (951 mg, 3.21 mmol) and O-allyl-N-(9-anthracenylmethyl)cinchonidinium bromide (95%, 0.205 g, 0.322 mmol) in dichloromethane (25 mL) was added cesium hydroxide monohydrate (0.647 g, 3.85 mmol). (See E. J. Corey et al., J. Am. Chem. Soc. 1997, 119, 12414-12415.) The reaction was stirred at −30° C. for 18 hours, then washed with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (Eluants: dichloromethane, then EtOAc) to give C5 as a gum. Yield: 1.63 g, 3.19 mmol, 99%. LCMS m/z 511.3 (M+1). 1H NMR (400 MHz, CDCl3) δ 1.39 (s, 9H), 3.24 (dd, half of ABX pattern, J=14.3, 8.2 Hz, 1H), 3.38 (br dd, half of ABX pattern, J=14.3, 4.6 Hz, 1H), 4.22 (dd, J=8.3, 4.6 Hz, 1H), 5.25 (AB quartet, JAB=14.6 Hz, ΔνAB=18.3 Hz, 2H), 6.72 (br d, J=7 Hz, 2H), 7.16-7.22 (m, 4H), 7.25-7.44 (m, 8H), 7.50-7.54 (m, 2H).

후처리

  1. washwashed with water
  2. dry with materialdried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by chromatography on silica gel (Eluants

출처 및 근거

ORD 기록
ord-098708fee0db4449951d8d80fcf2e5f2
출처 데이터셋
uspto-grants-2015_01
특허 번호
US08933095B2

연결된 노트

불러오는 중…