Chlorotrimethylsilane → HCID 178460555, compound

HRID 1062534Notes

Reaction equation

HRID 1062534 reaction equation
C1N2CCN(CC2)C1.I[C:10]1[CH2:14][CH2:13][CH:12]([OH:15])[CH:11]=1.C[Si](Cl)(C)C.[CH3:21][PH:22](=[O:27])[O:23][CH:24]([CH3:26])[CH3:25]>C1(C)C=CC=CC=1.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>[OH:15][CH:12]1[CH2:13][CH2:14][C:10]([CH2:21][PH:22](=[O:27])[O:23][CH:24]([CH3:26])[CH3:25])=[CH:11]1

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 9237DabcoHCID 11715443HCID 11715443, compoundHCID 178460552HCID 178460552, compound

Product 1

HCID 178460555HCID 178460555, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 1140TolueneSolvent

Procedure

To a solution of DABCO (11.8 g, 105 mmol) and 3-iodo-cyclopent-2-enol (5.5 g, 26.3 mmol) in anhydrous toluene (300 cm3) was added trimethylsilyl chloride (3 g, 27.6 mmol). The reaction mixture was stirred at room temperature for 15 min, after which time isopropyl methylphosphinate (4.8 g, 39.4 mmol) and tetrakis(triphenylphosphine)palladium(0) (760 mg, 2.5 mol %) were added. The reaction mixture was heated at 70° C. for 24 h after which time a second portion of tetrakis(triphenylphosphine)palladium(0) (760 mg, 2.5 mol %) was added and heating continued for a further 24 h. The reaction mixture was filtered while still hot and aqueous ethanol (50 cm3) added to the filtrate, which was then concentrated in vacuo. The product was isolated by short column vacuum chromatography on silica gel (15% ethanol/ethyl acetate) to yield the title compound (3) as a slightly coloured oil (3.5 g, 65%): 1H NMR (300 MHz, CDCl3) δ 1.25 (3H, t, J=6.4, OCHCH3), 1.327 and 1.333 (3H, 2×d, J=6.2 and 6.2 Hz, OCHCH3), 1.49 and 1.51 (3H, 2×d, J=14.4 and 14.4 Hz, PCH3), 1.76-1.92 (1H, m, C(5)—H), 2.33-2.52 (2H, m, C(5)—H′ and C(4)—H), 2.60-2.78 (1H, m, C(4)—H′), 4.55 (1H, m, OCHCH3), 4.95 (1H, m, C(3)—H), 6.57 (1H, m, C(2)—H); 13C NMR (75.46 MHz, CDCl3) δ 13.8 and 14.0 (PCH3, d, JPC=101 and 101 Hz), 23.88 and 23.91 (POCCH3, d, 3JPOCC=4.9 and 4.6 Hz), 24.31 (POCCH3, overlapping d, 3JPOCC=3.4 Hz) 26.89 and 26.91 (C(4), d, 3JPC=12.8 and 12.5 Hz), 29.27 and 29.35 (C(5), d, 2JPC=8.8 and 8.6 Hz), 76.94 and 73.65 (POCHCH3, d, 2JPOC=6.0 and 6.3 Hz), 76.94 and 77.18 (C(3), d, 3JPC=5.0 and 7.5 Hz), 138.11 and 138.22 (C(1), d, JPC=126 and 126 Hz), 147.54 (C(2), d, J=10.6 Hz), −P NMR (121 MHz, CDCl3) δ 38.9, 39.0, (ESI) 207.1154 (MH+-C9H20O3 requires 207.1150).

Workup

  1. additionwas added
  2. temperatureheating
  3. waitcontinued for a further 24 h
  4. filtrationThe reaction mixture was filtered while still hot and aqueous ethanol (50 cm3)
  5. additionadded to the filtrate, which
  6. concentrationwas then concentrated in vacuo
  7. customThe product was isolated by short column vacuum chromatography on silica gel (15% ethanol/ethyl acetate)

Sources & evidence

ORD record
ord-3db29df7c478465cad1653ec2bdc115b
Source dataset
uspto-grants-2005_11
Patent number
US06962907B2

Reaction notes

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