Tributylstannane → HCID 70873452, compound

HRID 713634Notes

Reaction equation

HRID 713634 reaction equation
O1CCCC1.[C:6]([C:8]1([OH:26])[C:19]([CH3:24])([C:20]([F:23])([F:22])[F:21])[CH2:18][C:11]2([O:15][CH:14]([CH3:16])[CH:13]([CH3:17])[O:12]2)[CH:10]=[C:9]1[CH3:25])#[CH:7].[CH2:27]([SnH:31]([CH2:36][CH2:37][CH2:38][CH3:39])[CH2:32][CH2:33][CH2:34][CH3:35])[CH2:28][CH2:29][CH3:30]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH3:17][CH:13]1[CH:14]([CH3:16])[O:15][C:11]2([CH2:18][C:19]([CH3:24])([C:20]([F:21])([F:23])[F:22])[C:8](/[CH:6]=[CH:7]/[Sn:31]([CH2:32][CH2:33][CH2:34][CH3:35])([CH2:36][CH2:37][CH2:38][CH3:39])[CH2:27][CH2:28][CH2:29][CH3:30])([OH:26])[C:9]([CH3:25])=[CH:10]2)[O:12]1

Participants

6

Reactant 3

HCID 5948TributylstannaneHCID 8028TetrahydrofuranHCID 86712502HCID 86712502, compound

Product 1

HCID 70873452HCID 70873452, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

Under argon, tetrakis(triphenylphosphine)palladium(0) (19 mg, 0.02 mmol) was initially charged in a round-bottom flask that had been dried by heating, and abs. tetrahydrofuran (5 ml) and 8-ethynyl-2,3,7,9-tetramethyl-9-(trifluoromethyl)-1,4-dioxaspiro[4.5]dec-6-en-8-ol (100 mg, 0.33 mmol) were added. Stirring at room temperature for 5 minutes was followed by the addition of tributyltin hydride (0.11 ml, 0.39 mmol). The resulting reaction mixture was stirred at 55° C. for 1 h and, after cooling to room temperature, water was added. The aqueous phase was repeatedly extracted thoroughly with dichloromethane, and the combined organic phases were then dried over magnesium sulfate, filtered and concentrated under reduced pressure. By final column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), it was possible to obtain 2,3,7,9-tetramethyl-8-[(E)-2-(tributylstannyl)vinyl]-9-(trifluoromethyl)-1,4-dioxaspiro[4.5]dec-6-en-8-ol (160 mg, 82% of theory) in the form of a colorless oil. 1H-NMR (400 MHz, CDCl3 δ, ppm) 6.33/6.31 (d, 1H), 5.97/5.92 (d, 1H), 5.51/5.42 (s, 1H), 4.24/3.64 (m, 2H), 2.46/2.35 (d, 1H), 1.92 (br. s, 1H, OH), 1.91/1.87 (d, 1H), 1.64/1.62 (s, 3H), 1.49 (m, 6H), 1.32-1.26 (m, 9H), 1.18 (m, 3H), 0.89 (m, 18H).

Workup

  1. customhad been dried
  2. temperatureby heating
  3. customThe resulting reaction mixture
  4. stirringwas stirred at 55° C. for 1 h
  5. temperatureafter cooling to room temperature
  6. extractionThe aqueous phase was repeatedly extracted thoroughly with dichloromethane
  7. dry with materialthe combined organic phases were then dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customBy final column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), it

Sources & evidence

ORD record
ord-5aba639a14464c23be57895c5b1916f4
Source dataset
uspto-grants-2015_11
Patent number
US09185914B2

Reaction notes

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