HCID 90310712, compound → HCID 90310894, compound

HRID 1519153Notes

Reaction equation

HRID 1519153 reaction equation
Br[C:2]1[CH:15]=[CH:14][CH:13]=[C:12]([F:16])[C:3]=1[O:4][Si:5]([C:8]([CH3:11])([CH3:10])[CH3:9])([CH3:7])[CH3:6].[Br-].[CH:18]1([Zn+])[CH2:21][CH2:20][CH2:19]1>CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C.C1COCC1>[CH:18]1([C:2]2[CH:15]=[CH:14][CH:13]=[C:12]([F:16])[C:3]=2[O:4][Si:5]([C:8]([CH3:11])([CH3:10])[CH3:9])([CH3:7])[CH3:6])[CH2:21][CH2:20][CH2:19]1

Participants

5

Reactant 2

HCID 90310712HCID 90310712, compoundHCID 178419766HCID 178419766, compound

Product 1

HCID 90310894HCID 90310894, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
45 °C

Procedure

A 1-L three-neck, round bottomed flask, equipped with a stir bar, temperature probe and nitrogen inlet was charged with (2-bromo-6-fluorophenoxy)(tert-butyl)dimethylsilane (27.2 g, 89.1 mmol), THF (181.2 mL) and bis(tri-tert-butylphosphine)palladium (3.4 g, 6.68 mmol). Cyclobutylzinc bromide (267.2 mL, 134 mmol) was added and the reaction is heated at 45° Celsius for 22 hours. The reaction was cooled to room temperature and quenched with 1M HCl. The aqueous phase is extracted with MTBE and the combined organic extracts were washed with water, saturated aqueous thiourea, 1M HCl brine, dried over sodium sulfate and concentrated to dryness to provide (2-cyclobutyl-6-fluorophenoxy)(tert-butyl)dimethylsilane as a light yellow oil (24.5 g, 98%). MS (EI): calcd. for C16H25FOSi, 280.5; m/z found 280.1 [M]. 1H NMR (400 MHz, CDCl3), δ 7.08-7.04 (m, 1H), 6.90-6.83 (m, 2H), 3.81 (tt, J=9.4, 7.8 Hz, 1H), 2.32 (dtd, J=10.3, 7.8, 2.4 Hz, 2H), 2.14-1.80 (m, 4H), 1.03 (s, 9H), 0.20 (s, 3H), 0.19 (s, 3H).

Workup

  1. customA 1-L three-neck, round bottomed flask, equipped with a stir bar
  2. temperatureThe reaction was cooled to room temperature
  3. customquenched with 1M HCl
  4. extractionThe aqueous phase is extracted with MTBE
  5. washthe combined organic extracts were washed with water, saturated aqueous thiourea, 1M HCl brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-f5ad22a381fd4976958d88da76d80037
Source dataset
uspto-grants-2015_07
Patent number
US09073876B2

Reaction notes

Loading…