Dimethylformamide → HCID 66890357, compound

HRID 250172Notes

Reaction equation

HRID 250172 reaction equation
[O:1]([C:9]1[CH:14]=[CH:13][C:12]([C:15]([C:20]2[CH:25]=[CH:24][C:23](OS(C(F)(F)F)(=O)=O)=[C:22]([CH3:34])[CH:21]=2)([CH2:18][CH3:19])[CH2:16][CH3:17])=[CH:11][C:10]=1[CH3:35])[Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3].CN(C=O)C.[CH3:41][C:42]([OH:46])([C:44]#[CH:45])[CH3:43]>CCOCC>[O:1]([C:9]1[CH:14]=[CH:13][C:12]([C:15]([C:20]2[CH:25]=[CH:24][C:23]([C:45]#[C:44][C:42]([CH3:43])([OH:46])[CH3:41])=[C:22]([CH3:34])[CH:21]=2)([CH2:18][CH3:19])[CH2:16][CH3:17])=[CH:11][C:10]=1[CH3:35])[Si:2]([C:5]([CH3:7])([CH3:8])[CH3:6])([CH3:4])[CH3:3]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 82582-Methyl-3-butyn-2-olHCID 86615356HCID 86615356, compound

Product 1

HCID 66890357HCID 66890357, compoundYield 32.3%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
65 °C

Procedure

To an oven-dried, argon-sparged flask was added Pd[PPh3]4 (46 mg) and anhyd Cul (15 mg). To the flask under argon was added a solution of trifluoromethanesulfonic acid 4-{1-[4-(tert-butyl-dimethylsiloxy)-3-methylphenyl]-1-ethyl-propyl}-2-methylphenyl ester (0.42 g, 0.80 mmol) in anhyd DMF (2.5 mL), TEA (0.56 mL, 4.0 mmol) and 2-methyl-3-butyn-2-ol (0.12 mL, 1.2 mmol). After heating at 65° C. for 15 h, the reaction mixture was diluted with Et2O (50 mL), washed with H2O (2×30 mL) and brine, then dried (Na2SO4) and concentrated under reduced pressure. The crude material was chromatographed (silica, EtOAc/Hex, 0:100 to 10:90) to afford the title compound (0.12 g, 32%) as an orange oil. 1H-NMR (CDCl3) δ 7.26 (1.4H, d, J=8.1), 7.01 (1H, d, J=1.8), 6.94 (1H, dd, J=1.8, 8.1), 6.85 (1H, d, J=2.3), 6.80 (1H, dd, J=2.3, 8.3), 6.63 (1H, d, J=8.3), 2.36 (3H, s), 2.14 (3H, s), 2.03 (4H, q, J=7.3), 1.63 (6H, s), 1.01 (9H, s), 0.59 (6H, t, J=7.3), 0.20 (6H, s); Rf=0.10 (silica, 1:9 EtOAct/Hx).

Workup

  1. customTo an oven-dried, argon-sparged flask
  2. additionwas added Pd[PPh3]4 (46 mg) and anhyd Cul (15 mg)
  3. washwashed with H2O (2×30 mL) and brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. customThe crude material was chromatographed (silica, EtOAc/Hex, 0:100 to 10:90)

Sources & evidence

ORD record
ord-b1c3f02adfd44b82bdc2f85d3030c9d3
Source dataset
uspto-grants-2011_01
Patent number
US07863298B2

Reaction notes

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