3-Butenoic acid → 5-(Triisopropylsilyl)-pent-3-enoic acid

HRID 2101657Notes

Reaction equation

HRID 2101657 reaction equation
[CH2:1]([Si:4]([CH:11]([CH3:13])[CH3:12])([CH:8]([CH3:10])[CH3:9])[CH:5]([CH3:7])[CH3:6])[CH:2]=[CH2:3].[C:14]([OH:19])(=[O:18])[CH2:15]C=C>CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3OC(C)C)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1.C(Cl)Cl>[CH:11]([Si:4]([CH:5]([CH3:6])[CH3:7])([CH:8]([CH3:10])[CH3:9])[CH2:1][CH:2]=[CH:3][CH2:15][C:14]([OH:19])=[O:18])([CH3:13])[CH3:12]

Participants

5

Reactant 2

HCID 327433-Butenoic acidHCID 5018111Allyltriisopropylsilane

Product 1

HCID 866132145-(Triisopropylsilyl)-pent-3-enoic acidYield 87%

Reagents, catalysts & solvents 2

HCID 11763533(1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)(dichloro)((2-((propan-2-yl)oxy)phenyl)methylidene)rutheniumCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

A flame dried round-bottomed flask was charged with allyltriisopropylsilane (0.722 mL, 3 mmol, 3 eq), 3-butenoic acid (0.084 mL, 1 mmol, 1 eq) and DCM (3 mL). Hoveyda-Grubbs' Catalyst (31 mg, 0.05 mmol, 0.05 eq) was subsequently added as a solid and the reaction was heated to reflux (40° C.) under an atmosphere of argon. After 3 days the reaction was concentrated under reduced pressure to give a dark brown oil. Column chromatography (hexane:ether, 85:15, to remove excess silane, then 50:50) gave 5-(triisopropylsilyl)-pent-3-enoic acid as a colourless oil (223 mg, 87% yield). For major isomer E: 1H NMR (400 MHz, CDCl3) δ 1.05-1.06 (m, 21H, Si(i−Pr)3), 1.61-1.63 (d, 2H, CH2Si(i−Pr)3, J=8.0 Hz), 3.04-3.06 (d, 2H, HOOCCH2, J=7 Hz), 5.37-5.45 (m, 1H, CH2CHCH), 5.62-5.70 (dt, CH2CHCH, J=15.1, 8.2 Hz), 11.41 (s, 1H, COOH); 13C NMR (50 MHz, CDCl3) δ 10.9 (Si(CH(CH3)2)3), 15.6 (CH2Si(i−Pr)3), 18.6 (Si(CH(CH3)2)3), 38.0 (HOOCCH2), 118.8 (CH2CHCH), 132.6 (CH2CHCH), 178.7 (HOOC). For minor isomer Z: 1H NMR (400 MHz, CDCl3) δ 1.05-1.06 (m, 21H, Si(i−Pr)3), 1.56-1.58 (d, 2H, CH2Si(i−Pr)3, J=8.6 Hz), 3.17-3.19 (d, 2H, HOOCCH2, J=7.8 Hz), 5.37-5.45 (m, 1H, CH2CHCH), 5.71-5.78 (m, CH2CHCH), 11.41 (s, 1H, COOH); 13C NMR (50 MHz, CDCl3) δ 11.0 (CH2Si(i−Pr)3), 11.1 (Si(CH(CH3)2)3), 18.6 (Si(CH(CH3)2)3), 32.5 (HOOCCH2), 117.5 (CH2CHCH), 130.7 (CH2CHCH), 178.6 (HOOC); IR (v, cm−1) 2867 (COO—H), 1713 (HOC═O), 660 (C—Si); HRMS required for C14H28O2Si: 256.1859, found 256.1866.

Workup

  1. temperaturethe reaction was heated
  2. concentrationAfter 3 days the reaction was concentrated under reduced pressure
  3. customto give a dark brown oil
  4. customColumn chromatography (hexane:ether, 85:15, to remove excess silane

Sources & evidence

ORD record
ord-3782e956bccb4f018934b4d436126e6f
Source dataset
uspto-grants-2009_08
Patent number
US07572928B2

Reaction notes

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