Ethyl Acetate → Tert-butyl 4'-(benzyloxy)-2'-nitrobiphenyl-4-ylcarbamate

HRID 1425562Notes

Reaction equation

HRID 1425562 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12](Cl)=[C:11]([N+:16]([O-:18])=[O:17])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC1(C)C(C)(C)OB([C:27]2[CH:32]=[CH:31][C:30]([NH:33][C:34](=[O:40])[O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[CH:29][CH:28]=2)O1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:27]2[CH:28]=[CH:29][C:30]([NH:33][C:34](=[O:40])[O:35][C:36]([CH3:38])([CH3:37])[CH3:39])=[CH:31][CH:32]=2)=[C:11]([N+:16]([O-:18])=[O:17])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 2734617tert-butyl N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamateHCID 110436225-Benzyloxy-2-chloro-nitrobenzene

Product 1

HCID 58160246Tert-butyl 4'-(benzyloxy)-2'-nitrobiphenyl-4-ylcarbamateYield 88%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To 4-(benzyloxy)-1-chloro-2-nitrobenzene (526 mg, 2 mmol) and tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate (670 mg, 2.1 mmol) in 12 mL dioxane was added 4 mL of a 1 M Na2CO3 (aq) solution and Tetrakis(triphenylphosphine)palladium (69 mg, 0.06 mmol). The suspension was heated at reflux for 15 h under Ar atmosphere and cooled to rt. It was added EtOAc (100 mL) and washed with brine (80 mL), water (80 mL), and dried over MgSO4. After solvent removal, the residue was chromatographed (hexane/EtOAc) to afford tert-butyl 4′-(benzyloxy)-2′-nitrobiphenyl-4-ylcarbamate as a yellow solid (740 mg, 88%). 1H NMR (400 MHz, CDCl3) δ 7.44-7.34 (m, 8H), (d, J=8.4 Hz, 1H), 7.20-7.16 (m, 3H), 6.50 (s, 1H), 5.12 (s, 2H), 1.51 (s, 9H); MS (ESI) m/z 443 (M+Na+).

Workup

  1. temperatureThe suspension was heated
  2. temperatureat reflux for 15 h under Ar atmosphere
  3. washwashed with brine (80 mL), water (80 mL)
  4. dry with materialdried over MgSO4
  5. customAfter solvent removal
  6. customthe residue was chromatographed (hexane/EtOAc)

Sources & evidence

ORD record
ord-c020371b875f46c798d08e40712dfc1a
Source dataset
uspto-grants-2015_01
Patent number
US08932557B2

Reaction notes

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