Triphenylphosphine → 5-bromo-2,2'-difluoro-6'-((S)-pent-4-en-2-yloxy)-1,1'-biphenyl

HRID 1400773Notes

Reaction equation

HRID 1400773 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:16])=[C:6]([C:8]2[C:9]([OH:15])=[CH:10][CH:11]=[CH:12][C:13]=2[F:14])[CH:7]=1.[CH3:17][C@@H:18](O)[CH2:19][CH:20]=[CH2:21].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:16])=[C:6]([C:8]2[C:9]([O:15][C@H:20]([CH2:19][CH:18]=[CH2:17])[CH3:21])=[CH:10][CH:11]=[CH:12][C:13]=2[F:14])[CH:7]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-olHCID 867108255'-Bromo-2',6-difluoro-[1,1'-biphenyl]-2-ol

Product 1

HCID 867108265-bromo-2,2'-difluoro-6'-((S)-pent-4-en-2-yloxy)-1,1'-biphenylYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

5′-Bromo-2′,6-difluoro-[1,1′-biphenyl]-2-ol (520 mg, 1.82 mmol., 1.0 equiv) were mixed with (R)-pent-4-en-2-ol (314 mg, 3.65 mmol, 2.0 equiv) and Ph3P (957 mg, 3.65 mmol, 2.0 equiv) in THF (6 mL). To this solution was added DEAD (1661 μl, 3.65 mmol, 2.0 equiv) dropwise and stirred overnight. The solution was mixed with silica gel and concentrated and purified by 40 g ISCO column with 0-10% EtOAc/hexane to afford 5-bromo-2,2′-difluoro-6′-((S)-pent-4-en-2-yloxy)-1,1′-biphenyl (500 mg, 78%). 1H NMR (400 MHz, CDCl3) δ 7.52-7.42 (m, 2H), 7.34-7.28 (m, 1H), 7.03 (t, J=9.0 Hz, 1H), 6.81-6.74 (m, 2H), 5.81-5.62 (m, 1H), 5.12-4.96 (m, 2H), 4.41 (dq, J=11.7, 5.9 Hz, 1H), 2.44-2.18 (m, 2H), 1.23 (dd, J=7.3, 6.3 Hz, 3H). LCMS (M+1)=353.1.

Workup

  1. additionThe solution was mixed with silica gel
  2. concentrationconcentrated
  3. custompurified by 40 g ISCO column with 0-10% EtOAc/hexane

Sources & evidence

ORD record
ord-d94901e8bea146cd8b2ba46ece17a3b7
Source dataset
uspto-grants-2014_12
Patent number
US08906929B2

Reaction notes

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