3,5-Bis(trifluoromethyl)styrene → benzyl {(1R,5E)-6-[3,5-bis(trifluoromethyl)phenyl]-1-[2-bromo-5-(trifluoromethyl)phenyl]hex-5-en-1-yl}carbamate

HRID 529709Notes

Reaction equation

HRID 529709 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[C@@H:12]([NH:18][C:19](=[O:28])[O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[CH2:13][CH2:14][CH2:15][CH:16]=[CH2:17].C([C:31]1[CH:36]=[C:35]([C:37]([F:40])([F:39])[F:38])[CH:34]=[C:33]([C:41]([F:44])([F:43])[F:42])[CH:32]=1)=C>CC1C=C(C)C=C(C)C=1N1CCN(C2C(C)=CC(C)=CC=2C)C1=[Ru-4](Cl)(Cl)=CC1C=C(S(N(C)C)(=O)=O)C=CC=1OC(C)C.ClCCl>[F:38][C:37]([F:39])([F:40])[C:35]1[CH:36]=[C:31](/[CH:17]=[CH:16]/[CH2:15][CH2:14][CH2:13][C@@H:12]([NH:18][C:19](=[O:28])[O:20][CH2:21][C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[C:3]2[CH:4]=[C:5]([C:8]([F:11])([F:10])[F:9])[CH:6]=[CH:7][C:2]=2[Br:1])[CH:32]=[C:33]([C:41]([F:42])([F:43])[F:44])[CH:34]=1

Participants

5

Reactant 2

HCID 27732423,5-Bis(trifluoromethyl)styreneHCID 86682275benzyl {(1S)-1-[2-bromo-5-(trifluoromethyl)phenyl]hex-5-en-1-yl}carbamate

Product 1

HCID 86682274benzyl {(1R,5E)-6-[3,5-bis(trifluoromethyl)phenyl]-1-[2-bromo-5-(trifluoromethyl)phenyl]hex-5-en-1-yl}carbamateYield 90.9%

Reagents, catalysts & solvents 2

HCID 178425455HCID 178425455, compoundCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

To a 100 mL RBF equipped with a reflux condenser was added benzyl {(1S)-1-[2-bromo-5-(trifluoromethyl)phenyl]hex-5-en-1-yl}carbamate (1.5 g, 3.29 mmol), 1-ethenyl-3,5-bis(trifluoromethyl)benzene (1.58 g, 6.57 mmol) and dichloromethane (10 mL). The system was flushed with nitrogen and 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (41 mg, 0.57 mmol) was added before heating at 60° C. for 20 min. The reaction was cooled to room temperature and was directly purified by column chromatography to yield benzyl {(1R,5E)-6-[3,5-bis(trifluoromethyl)phenyl]-1-[2-bromo-5-(trifluoromethyl)phenyl]hex-5-en-1-yl}carbamate (2.0 g, 2.99 mmol). 1H NMR (500 MHz, CDCl3) δ7.81 (s, 1H), 7.67 (d, J=8.3 Hz, 1H), 7.37 (d, J=8.1 Hz, 1H), 5.82 (m, 1H), 5.05 (m, 2H), 4.41 (m, 1H), 3.82 (s, 1H), 2.13 (m, 2H), 1.76 (m, 1H), 1.42 (m, 1H).

Workup

  1. customTo a 100 mL RBF equipped with a reflux condenser
  2. additionwas added
  3. temperatureThe reaction was cooled to room temperature
  4. customwas directly purified by column chromatography

Sources & evidence

ORD record
ord-47b6d86398aa485a99a164ab7c789273
Source dataset
uspto-grants-2016_05
Patent number
US09346825B2

Reaction notes

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