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

HRID 1426272

Reaktionsgleichung

Reaktionsgleichung von HRID 1426272
[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

Komponenten

6

Edukt 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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
-30 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-098708fee0db4449951d8d80fcf2e5f2
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08933095B2

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