Methoxymethyl-triphenylphosphonium chloride → 6-Fluoro-2-(2-methoxyvinyl)-8-(triisopropylsilyloxy)quinoline

HRID 1095755Notes

Reaction equation

[Cl-].[CH3:2][O:3][CH2:4][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:24]C([O-])(C)C.[K+].[F:30][C:31]1[CH:32]=[C:33]2[C:38](=[C:39]([O:41][Si:42]([CH:49]([CH3:51])[CH3:50])([CH:46]([CH3:48])[CH3:47])[CH:43]([CH3:45])[CH3:44])[CH:40]=1)[N:37]=[C:36](C=O)[CH:35]=[CH:34]2>C1COCC1>[F:30][C:31]1[CH:32]=[C:33]2[C:38](=[C:39]([O:41][Si:42]([CH:43]([CH3:45])[CH3:44])([CH:46]([CH3:47])[CH3:48])[CH:49]([CH3:50])[CH3:51])[CH:40]=1)[N:37]=[C:36]([CH:24]=[CH:4][O:3][CH3:2])[CH:35]=[CH:34]2

Participants

Conditions

Temperature: 0 °C

Procedure

(Methoxymethyl)triphenylphosphonium chloride (8.355 g, 24.37 mmol) was dissolved in THF (130 mL), cooled to 0° C., and treated dropwise with a solution of 1M KOtBu in THF (26.5 ml, 26.5 mmol). The mixture was warmed and stirred at ambient temperature for 15 minutes. A solution of 6-fluoro-8-(triisopropylsilyloxy)quinoline-2-carbaldehyde (7.70 g, 22.1 mmol) dissolved in THF (15 mL) was added. The reaction was stirred at ambient temperature for 10 hours. The mixture was concentrated in vacuo and applied directly to a column of SiO2 eluting with a stepped gradient from 1-4% Et2O/hexanes, (4.75 g). 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J=8.6 Hz, 1H), 7.74 (d, J=13 Hz, 1H), 7.23 (d, J=8.6 Hz, 1H), 6.93 (dd, J1=2.8 Hz, J2=8.7 Hz, 1H), 6.88 (dd, J1=2.7 Hz, J2=10.2 Hz, 1H), 6.02 (d, J=12.5 Hz, 1H), 3.77 (s, 3H), 1.47-1.38 (m, 3H), 1.15 (d, 18H).

Workup

temperatureThe mixture was warmed
additionwas added
stirringThe reaction was stirred at ambient temperature for 10 hours
concentrationThe mixture was concentrated in vacuo

Sources & evidence

ORD record: ord-fb53dc39fd0c4791839a5479a3a3e622
Source dataset: uspto-grants-2012_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08138181B2

Reaction notes

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