Potassium Carbonate → (E)-ethyl 3-(3-(tert-butoxycarbonylamino)-4-chlorophenyl)acrylate

HRID 2167661Notes

Reaction equation

HRID 2167661 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([Cl:16])=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:7]=1.C([O-])([O-])=O.[K+].[K+].CC1(C)C(C)(C)OB(/[CH:31]=[CH:32]/[C:33]([O:35][CH2:36][CH3:37])=[O:34])O1>C(#N)C.CCO.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>[C:11]([O:10][C:9]([NH:8][C:6]1[CH:7]=[C:2](/[CH:31]=[CH:32]/[C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:3]=[CH:4][C:5]=1[Cl:16])=[O:15])([CH3:14])([CH3:13])[CH3:12]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 23553751(E)-Ethyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acrylateHCID 57840526tert-butyl N-(5-bromo-2-chlorophenyl)carbamate

Product 1

HCID 67067541(E)-ethyl 3-(3-(tert-butoxycarbonylamino)-4-chlorophenyl)acrylate

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of tert-butyl 5-bromo-2-chlorophenylcarbamate (6-1) (1.0 equiv.) in acetonitrile (0.3 M) and EtOH (0.5 M) was added K2CO3 (2.0 equiv.). The reaction was degassed and flushed with N2, then added (E)-ethyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acrylate (6-2) (1.2 equiv.) and Pd(PPh3)4 (0.1 equiv.). The reaction was flushed again with N2 and stirred at 100° C. overnight. After cooling to room temperature, hexane was added, and the mixture was filtered through a pad of silica, eluting with EA/Hex (1:1) until the product was completely eluted. The filtrate was concentrated and purified on Combiflash, eluting with 0-15% EA in Hex to give (E)-ethyl 3-(3-(tert-butoxycarbonylamino)-4-chlorophenyl)acrylate (6-3) as a white solid.

Workup

  1. customThe reaction was degassed
  2. customflushed with N2
  3. customThe reaction was flushed again with N2
  4. temperatureAfter cooling to room temperature
  5. additionhexane was added
  6. filtrationthe mixture was filtered through a pad of silica
  7. washeluting with EA/Hex (1:1) until the product
  8. washwas completely eluted
  9. concentrationThe filtrate was concentrated
  10. custompurified on Combiflash
  11. washeluting with 0-15% EA in Hex

Sources & evidence

ORD record
ord-6390960d0f6149fab0482fb3a9622928
Source dataset
uspto-grants-2015_06
Patent number
US09045470B2

Reaction notes

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