Diisopropylamine → HCID 86620322, compound

HRID 1176958Notes

Reaction equation

HRID 1176958 reaction equation
[O:1]1[CH2:6][CH2:5][O:4]CC1.N([CH:11]([CH3:13])[CH3:12])C(C)C.Br[C:15]1[CH:20]=[CH:19][C:18]([C:21]([C:23]([C:25]2[CH:30]=[CH:29][C:28](Br)=[CH:27][CH:26]=2)=O)=O)=[CH:17][CH:16]=1.[C:32]([C:34]1[CH:39]=[CH:38][C:37]([C:40]([F:43])([F:42])[F:41])=[CH:36][CH:35]=1)#[CH:33]>C(OCC)(=O)C.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.[Cu]I.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C>[F:41][C:40]([F:43])([F:42])[C:15]1[CH:20]=[CH:19][C:18]([C:21]#[C:23][C:25]2[CH:30]=[CH:29][C:28]([C:5](=[O:4])[C:6]([C:12]3[CH:11]=[CH:13][C:34]([C:33]#[C:32][C:34]4[CH:39]=[CH:38][C:37]([C:40]([F:41])([F:42])[F:43])=[CH:36][CH:35]=4)=[CH:32][CH:33]=3)=[O:1])=[CH:27][CH:26]=2)=[CH:17][CH:16]=1

Participants

9

Reactant 4

HCID 7912DiisopropylamineHCID 312751,4-DioxaneHCID 964304,4'-DibromobenzilHCID 43482951-Ethynyl-4-(trifluoromethyl)benzene

Product 1

HCID 86620322HCID 86620322, compoundYield 74%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

In a glove box, a schlenk tube was charged with Pd(PhCN)2Cl2 (63 mg, 0.16 mmol) and CuI (21 mg, 0.11 mmol). Under argon counterflow, anhydrous dioxane (50 mL), P(t-Bu)3 (2.7 mL of 0.123 M solution in toluene, 0.33 mmol), HN(i-Pr)2 (1.8 mL, 13 mmol), 4,4′-dibromobenzil (2.0 g, 5.4 mmol), and 4-ethynyl-α,α,α-trifluorotoluene (2.31 g, 13.6 mmol) were added to the schlenk tube sequentially. After stirring at room temperature overnight, the reaction mixture was diluted with ethyl acetate and filtered through a pad of celite with EtOAc rinsing. The solvent was removed under reduced pressure and the product was purified by column chromatography (silica gel, hexanes:dichloromethane=3:1 (v/v), then hexanes:dichloromethane=1:1 (v/v)) to give light yellow needles (2.20 g, 74%). 1H NMR (300 MHz, CDCl3, δ): 7.98 (d, J=8.3 Hz, 4H), 7.64 (d, J=8.3 Hz, 2H), 7.64-7.60 (m, 8H). HRMS-FAB (m/z): [M+H]+ calcd for C32H17O2F6, 547.1133; found, 547.1146. Anal. Calcd for C32H16F6O2: C, 70.33; H, 2.95; F, 20.86. Found: C, 70.07; H, 2.81; F, 20.71.

Workup

  1. filtrationfiltered through a pad of celite with EtOAc rinsing
  2. customThe solvent was removed under reduced pressure
  3. customthe product was purified by column chromatography (silica gel, hexanes

Sources & evidence

ORD record
ord-00d53997f7824d60a8baabc30277e5cc
Source dataset
uspto-grants-2010_11
Patent number
US07842830B2

Reaction notes

Loading…