Tributylstannane → 2,3,7,9,9-Pentamethyl-8-[(E)-2-(tributylstannyl)vinyl]-1,4-dioxaspiro[4.5]dec-6-en-8-ol

HRID 713632Notes

Reaction equation

HRID 713632 reaction equation
O1CCCC1.[C:6]([C:8]1([OH:23])[C:19]([CH3:21])([CH3:20])[CH2:18][C:11]2([O:15][CH:14]([CH3:16])[CH:13]([CH3:17])[O:12]2)[CH:10]=[C:9]1[CH3:22])#[CH:7].[CH2:24]([SnH:28]([CH2:33][CH2:34][CH2:35][CH3:36])[CH2:29][CH2:30][CH2:31][CH3:32])[CH2:25][CH2:26][CH3:27]>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>[CH3:16][CH:14]1[CH:13]([CH3:17])[O:12][C:11]2([CH2:18][C:19]([CH3:21])([CH3:20])[C:8](/[CH:6]=[CH:7]/[Sn:28]([CH2:29][CH2:30][CH2:31][CH3:32])([CH2:33][CH2:34][CH2:35][CH3:36])[CH2:24][CH2:25][CH2:26][CH3:27])([OH:23])[C:9]([CH3:22])=[CH:10]2)[O:15]1

Participants

6

Reactant 3

HCID 5948TributylstannaneHCID 8028TetrahydrofuranHCID 731711598-Ethynyl-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-ol

Product 1

HCID 708734232,3,7,9,9-Pentamethyl-8-[(E)-2-(tributylstannyl)vinyl]-1,4-dioxaspiro[4.5]dec-6-en-8-olYield 69.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

Under argon, tetrakis(triphenylphosphine)palladium(0) (231 mg, 0.20 mmol) was initially charged in a round-bottom flask that had been dried by heating, and abs. tetrahydrofuran (25 ml) and 8-ethynyl-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-ol (1.0 g, 3.99 mmol) were added. Stirring at room temperature for 5 minutes was followed by the addition of tributyltin hydride (1.29 ml, 4.79 mmol). The resulting reaction mixture was stirred at room temperature for 1 h and then 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 2,3,7,9,9-pentamethyl-8-[(E)-2-(tributylstannyl)vinyl]-1,4-dioxaspiro[4.5]dec-6-en-8-ol (1.50 g, 66% of theory) in the form of a colorless oil. 1H-NMR (400 MHz, CDCl3 δ, ppm) 6.13 (d, 1H), 5.93 (d, 1H), 5.42 (s, 1H), 4.22/3.63 (m, 2H), 1.61 (s, 3H), 1.59 (d, 1H), 1.52 (d, 1H), 1.49 (m, 6H), 1.32-1.24 (m, 12H), 1.09 (s, 3H), 0.89 (m, 18H).

Workup

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

Sources & evidence

ORD record
ord-114ad221b2db468eb268aef740446879
Source dataset
uspto-grants-2015_11
Patent number
US09185914B2

Reaction notes

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