Potassium Carbonate → tert-butyl[(2S,3E)-1-{[tert-butyl(diphenyl)silyl]oxy}-4-(2-nitrophenyl)but-3-en-2-yl]carbamate

HRID 714127

Reaction equation

HRID 714127 reaction equation
[C:1]([O:5][C:6](=[O:30])[NH:7][C@@H:8]([CH:28]=O)[CH2:9][O:10][Si:11]([C:24]([CH3:27])([CH3:26])[CH3:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH3:4])([CH3:3])[CH3:2].[Br-].[N+:32]([C:35]1[CH:60]=[CH:59][CH:58]=[CH:57][C:36]=1[CH2:37][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O-:34])=[O:33].[PH4+].C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>COCCOC.C(Cl)Cl>[C:1]([O:5][C:6](=[O:30])[NH:7][C@@H:8](/[CH:28]=[CH:37]/[C:36]1[CH:57]=[CH:58][CH:59]=[CH:60][C:35]=1[N+:32]([O-:34])=[O:33])[CH2:9][O:10][Si:11]([C:24]([CH3:25])([CH3:26])[CH3:27])([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH3:3])([CH3:4])[CH3:2]

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 5460504PhosphoniumHCID 10885283(2-Nitrobenzyl)triphenylphosphonium bromideHCID 89929680tert-butyl[(2R)-1-{[tert-butyl(diphenyl)silyl]oxy}-3-oxopropan-2-yl]carbamate

Product 1

HCID 131734057tert-butyl[(2S,3E)-1-{[tert-butyl(diphenyl)silyl]oxy}-4-(2-nitrophenyl)but-3-en-2-yl]carbamateYield 38.1%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of tert-butyl[(2R)-1-{[tert-butyl(diphenyl)silyl]oxy}-3-oxopropan-2-yl]carbamate (3, 3.12 g, 7.3 mmol) in DME (30 ml) was treated with solid (2-nitrobenzyl)(triphenyl)phosphonium bromide(3.76 g, 7.86 mmol) (or any other suitable phosphonium salt), the mixture stirred at room temperature under N2 atmosphere for 30 min and then the reaction flask was charged with a solid mixture of potassium carbonate (1.78 g, 12.86 mmol) and 18-crown-6 (219 mg, 0.83 mmol). The purple mixture was further stirred at the same temperature for 14 h; diluted with DCM, washed with saturated NaHCO3, dried over MgSO4, filtered and concentrated Purified through a chromatographic cartridge of silicagel (50 g) eluted with 10% to 35% EtOAc in hexane to get 1.52 g (38% yield) of title compound as light yellow oil. MS: m/z=569.2 (MNa+).

Workup

  1. stirringThe purple mixture was further stirred at the same temperature for 14 h
  2. washwashed with saturated NaHCO3
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurified through a chromatographic cartridge of silicagel (50 g)
  7. washeluted with 10% to 35% EtOAc in hexane

Sources & evidence

ORD record
ord-13cfa7bc3a9f4e0a87920188b63cd6d6
Source dataset
uspto-grants-2015_11
Patent number
US09187415B2

Linked notes

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