Triphenylphosphine → 4-[((1S)-2-(benzyloxy)-1-{[(triisopropylsilyl)oxy]methyl}ethyl)oxy]-4'-(trifluoromethoxy)-1,1'-biphenyl

HRID 1496908Notes

Reaction equation

HRID 1496908 reaction equation
[CH2:1]([O:8][CH2:9][C@@H:10]([OH:23])[CH2:11][O:12][Si:13]([CH:20]([CH3:22])[CH3:21])([CH:17]([CH3:19])[CH3:18])[CH:14]([CH3:16])[CH3:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[F:24][C:25]([F:41])([F:40])[O:26][C:27]1[CH:32]=[CH:31][C:30]([C:33]2[CH:38]=[CH:37][C:36](O)=[CH:35][CH:34]=2)=[CH:29][CH:28]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1>[CH2:1]([O:8][CH2:9][C@H:10]([O:23][C:36]1[CH:35]=[CH:34][C:33]([C:30]2[CH:31]=[CH:32][C:27]([O:26][C:25]([F:24])([F:40])[F:41])=[CH:28][CH:29]=2)=[CH:38][CH:37]=1)[CH2:11][O:12][Si:13]([CH:14]([CH3:16])[CH3:15])([CH:20]([CH3:22])[CH3:21])[CH:17]([CH3:19])[CH3:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 120087344-(4-Trifluoromethoxyphenyl)phenolHCID 66707553(2R)-1-(benzyloxy)-3-[(triisopropylsilyl)oxy]-2-propanol

Product 1

HCID 547569974-[((1S)-2-(benzyloxy)-1-{[(triisopropylsilyl)oxy]methyl}ethyl)oxy]-4'-(trifluoromethoxy)-1,1'-biphenylYield 75.4%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
20 °C

Procedure

1,1′-Diisopropyl azodicarboxylate (7.70 mL, 0.039 mol) was added dropwise at 5° C. to a solution of the alcohol 79 (12.40 g, 0.037 mol), 4′-(trifluoromethoxy)[1,1′-biphenyl]-4-ol (reported by Edsall et al., 2003, via Suzuki coupling of 4-bromophenol and boronic acid 44) (8.29 g, 0.033 mol) and triphenylphosphine (10.26 g, 0.039 mol) in anhydrous benzene (25 mL) and the solution was stirred at 20° C. for 18 h. The product was adsorbed directly onto silica by concentration under reduced pressure, and chromatography on silica gel, eluting with EtOAc/petroleum ether (1:19), gave 4-[((1S)-2-(benzyloxy)-1-{[(triisopropylsilyl)oxy]methyl}ethyl)oxy]-4′-(trifluoromethoxy)-1,1′-biphenyl (80) (14.30 g, 69%) as a colourless oil: [α]19 +5.9° (c, 6.95, CHCl3); 1H NMR (CDCl3) δ 7.72 (d, J=8.8 Hz, 2H), 7.58 (d, J=8.8 Hz, 2H), 7.40 (d, J=8.8 Hz, 2H), 7.35-7.24 (m, 5H), 7.06 (d, J=8.8 Hz, 2H), 4.64-4.57 (m, 1H), 4.52 (s, 2H), 3.98-3.87 (m, 2H), 3.76-3.65 (m, 2H), 1.08-0.98 (m, 21H). APCI MS m/z 576 [M+H]+.

Workup

  1. concentrationThe product was adsorbed directly onto silica by concentration under reduced pressure, and chromatography on silica gel
  2. washeluting with EtOAc/petroleum ether (1:19)

Sources & evidence

ORD record
ord-8697bc7356d04032b7cf0963642da47e
Source dataset
uspto-grants-2015_12
Patent number
US09198913B2

Reaction notes

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