Dichloromethane → tert-Butyl(3S)-3-(tert-butoxycarbonylamino)-5-(2-methyl-5-nitro-phenyl)pent-4-enoate
Reaction equation
[I-].[C:2]([O:6][C:7](=[O:38])[CH2:8][C@H:9]([NH:30][C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:10][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([CH3:5])([CH3:4])[CH3:3].[CH3:39][C:40]1[CH:47]=[CH:46][C:45]([N+:48]([O-:50])=[O:49])=[CH:44][C:41]=1[CH:42]=O.C(Cl)Cl.CC(C)([O-])C.[K+]>O1CCCC1.O=[Mn]=O>[C:34]([O:33][C:31]([NH:30][C@H:9]([CH:10]=[CH:42][C:41]1[CH:44]=[C:45]([N+:48]([O-:50])=[O:49])[CH:46]=[CH:47][C:40]=1[CH3:39])[CH2:8][C:7]([O:6][C:2]([CH3:5])([CH3:4])[CH3:3])=[O:38])=[O:32])([CH3:37])([CH3:36])[CH3:35]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Procedure
Adapting a literature procedure (Jandeleit et al., U.S. Pat. No. 8,168,617 (2012)), tert-butyl(3S)-3-(tert-butoxycarbonylamino)-5-(2-methyl-5-nitro-phenyl)pent-4-enoate (18b) is prepared from [(2S)-4-tert-butoxy-2-(tert-butoxycarbonylamino)-4-oxo-butyl]-triphenyl-phosphonium iodide (18a) (1.30 g, 2.0 mmol), 2-methyl-5-nitro-benzaldehyde (1b) (495 mg, 3.0 mmol) (commercial or prepared in two steps from commercial 2-methyl-5-nitro benzoic acid (i) BH3.SMe2, THF, reflux, ii) MnO2, DCM, room temperature) as described in Example 1) with a commercial ˜1.0 M solution of potassium tert-butoxide (KOtBu) (3.0 mL, 3.0 mmol) in anhydrous tetrahydrofuran (THF) (10 mL) at with gradual warming from 0° (ice bath) to room temperature for 24 hours. Aqueous work and purification by silica gel column chromatography furnish the title compound (18b) as a mixture of geometric isomers ((E)/(Z)-isomers).
Workup
- customAqueous work and purification by silica gel column chromatography
Sources & evidence
- ORD record
- ord-a2fc7e2752dc40c1a1b7ddb0d5f5892f
- Source dataset
- uspto-grants-2016_07
- Patent number
- US09394237B2
Reaction notes
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