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

HRID 1426272Notes

Reaction equation

HRID 1426272 reaction equation
[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

Participants

6

Reactant 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

Product 1

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

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-30 °C

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-098708fee0db4449951d8d80fcf2e5f2
Source dataset
uspto-grants-2015_01
Patent number
US08933095B2

Reaction notes

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