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

HRID 1400776Notes

Reaction equation

HRID 1400776 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:16])=[C:6]([C:8]2[C:9]([OH:15])=[CH:10][CH:11]=[CH:12][C:13]=2[Cl: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]([CH3:16])=[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[Cl:14])[CH:7]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-olHCID 867108285'-Bromo-6-chloro-2'-methyl-[1,1'-biphenyl]-2-ol

Product 1

HCID 867108295-bromo-2'-chloro-2-methyl-6'-((S)-pent-4-en-2-yloxy)-1,1'-biphenylYield 52.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

5′-Bromo-6-chloro-2′-methyl-[1,1′-biphenyl]-2-ol (540 mg, 1.82 mmol, 1.0 equiv) were mixed with (R)-pent-4-en-2-ol (313 mg, 3.63 mmol, 2.0 equiv) and Ph3P (952 mg, 3.63 mmol, 2.0 equiv) in THF (6 ml). To this solution was added DEAD (1653 μl, 3.63 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/hex to afford 5-bromo-2′-chloro-2-methyl-6′-((S)-pent-4-en-2-yloxy)-1,1′-biphenyl (350 mg, 52.7%). 1H NMR (400 MHz, CDCl3) δ 7.39 (dd, J=8.2, 2.1 Hz, 1H), 7.25-7.21 (m, 2H), 7.14 (d, J=7.5 Hz, 1H), 7.07 (d, J=8.0 Hz, 1H), 6.86 (dd, J=8.0, 5.3 Hz, 1H), 5.66-5.50 (m, 1H), 5.05-4.90 (m, 2H), 4.35-4.24 (m, 1H), 2.30-2.12 (m, 2H), 2.01 (s, 3H), 1.16 (dd, J=11.0, 6.0 Hz, 3H). LCMS (M+1)=365.0.

Workup

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

Sources & evidence

ORD record
ord-4e81f14299574c2797ff3278128d5cdf
Source dataset
uspto-grants-2014_12
Patent number
US08906929B2

Reaction notes

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