Dichloromethane → HCID 86713137, compound

HRID 713617Notes

Reaction equation

HRID 713617 reaction equation
[OH:1][C:2]1([C:17]#[C:18]/[C:19](/[CH2:26][CH2:27][CH3:28])=[CH:20]\[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:13]([CH3:15])([CH3:14])[CH2:12][C:5]2([O:9][CH:8]([CH3:10])[CH:7]([CH3:11])[O:6]2)[CH:4]=[C:3]1[CH3:16].ClCCl.C(O[SiH](OCC)OCC)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CC#N.CC#N.CC#N.[CH]1[CH][CH][CH][CH]1.F[P-](F)(F)(F)(F)F.[Ru+].[Cu]I.O.O1CCCC1.C(OCC)C>[OH:1][C:2]1(/[CH:17]=[CH:18]/[C:19](/[CH2:26][CH2:27][CH3:28])=[CH:20]\[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:13]([CH3:14])([CH3:15])[CH2:12][C:5]2([O:9][CH:8]([CH3:10])[CH:7]([CH3:11])[O:6]2)[CH:4]=[C:3]1[CH3:16]

Participants

10

Reactant 4

HCID 6344DichloromethaneHCID 13830TriethoxysilaneHCID 2724141Tetrabutylammonium FluorideHCID 86713138HCID 86713138, compound

Product 1

HCID 86713137HCID 86713137, compoundYield 41%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178464408HCID 178464408, compoundCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Under argon, ethyl (2Z)-3-[(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-yl)ethynyl]-hex-2-enoate (340 mg, 0.87 mmol) was dissolved in a round-bottom flask in abs. dichloromethane (4 ml), and triethoxysilane (172 mg, 1.05 mmol) was added. The reaction solution was then cooled to 0° C., tris(acetonitrile)cyclopentadienylruthenium(II) hexafluorophosphate (18 mg, 0.04 mmol) was added and the mixture was stirred at room temperature for 2 h. Diethyl ether was then added, and the reaction mixture was concentrated under reduced pressure. The residue that remained was dissolved in abs. tetrahydrofuran (4 ml), copper(I) iodide (16 mg, 0.09 mmol) and tetra-n-butylammonium fluoride (289 mg, 1.11 mmol) were added, the mixture was stirred at room temperature for 4 h, and water was then added. The aqueous phase was repeatedly extracted thoroughly with dichloromethane. The combined organic phases were then dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient) gave ethyl (2Z)-3-[(E)-2-(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]-dec-6-en-8-yl)vinyl]hex-2-enoate (140 mg, 41% of theory) in the form of a colorless oil. 1H-NMR (400 MHz, CDCl3 δ, ppm) 7.68 (d, 1H), 6.09 (d, 1H), 5.97 (s, 1H), 5.48 (s, 1H), 4.19 (m, 3H), 3.61 (m, 1H), 2.29 (m, 1H), 2.22 (m, 2H), 2.02 (m, 1H), 1.92 (m, 3H), 1.67 (m, 2H), 1.62 (m, 1H), 1.28 (m, 6H), 1.20-1.08 (m, 9H), 0.91 (t, 3H).

Workup

  1. concentrationthe reaction mixture was concentrated under reduced pressure
  2. dissolutionThe residue that remained was dissolved in abs
  3. stirringthe mixture was stirred at room temperature for 4 h
  4. extractionThe aqueous phase was repeatedly extracted thoroughly with dichloromethane
  5. dry with materialThe combined organic phases were then dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customPurification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient)

Sources & evidence

ORD record
ord-667abcc221444d21ac41d63083e62f4a
Source dataset
uspto-grants-2015_11
Patent number
US09185914B2

Reaction notes

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