Triethylamine → HCID 178476814, compound

HRID 1062527Notes

Reaction equation

HRID 1062527 reaction equation
[OH:1][CH:2]1[CH2:6][CH2:5][C:4]([CH2:7][CH2:8][CH2:9][CH2:10][PH:11](=[O:15])[O:12][CH2:13][CH3:14])=[CH:3]1.[Si:16](Cl)([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17].C(N(CC)CC)C>CN(C=O)C.CN(C1C=CN=CC=1)C>[Si:16]([O:1][CH:2]1[CH2:6][CH2:5][C:4]([CH2:7][CH2:8][CH2:9][CH2:10][PH:11](=[O:15])[O:12][CH2:13][CH3:14])=[CH:3]1)([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 28928tert-Butyldimethylsilyl chlorideHCID 178476813HCID 178476813, compound

Product 1

HCID 178476814HCID 178476814, compoundYield 61.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of (±)-ethyl (3-hydroxycyclopentenyl)butylphosphinate (7) (3.66 g, 15.8 mmol) in anhydrous DMF (100 cm3) was treated with t-butyldimethylsilyl chloride (2.62 g, 17.4 mmol), triethylamine (4.55 cm3) and DMAP (425 mg). The reaction mixture was stirred at room temperature for 16 h, after which time the solvent was removed in vacuo. The residue was partitioned between DCM (50 cm3) and water (30 cm3) and the aqueous layer was further extracted with DCM (3×20 cm3). The combined organic layers were washed with water (2×30 cm3) and brine (40 cm3), dried over anhydrous sodium sulfate, filtered and the solvent removed under reduced pressure. The crude product was purified by short column vacuum chromatography on silica gel (15% ethanol/ethyl acetate) to yield the desired title compound (8) as a colourless oil (3.35 g, 61%): 1H-NMR (300 MHz, CDCl3) δH 0.09 (6H, s, Si(CH3)2), 0.89 (9H, s, SiC(CH3)3), 0.91 and 0.93 (3H, 2×d, J=7.2 and 7.2 Hz, PCH2CH2CH2CH3), 1.22-1.83 (9H, m, POCH2CH3, PCH2CH2CH2CH3, PCH2CH2CH2CH3, PCH2CH2CH2CH3), 2.26-2.72 (4H, m, C(4)—H, C(4)—H′, C(5)—H and C(5)—H′), 3.84-4.19 (2H, m, POCH2CH3), 4.97 (1H, m, C(3)—H), 6.50 and 6.54 (1H, 2×d, J=9.6 and 9.6 Hz, C(2)—H); 13C-NMR (75 MHz, CDCl3) δC −4.81 and −4.74 (d, 6JPC=5.7 Hz, Si(CH3)2), 13.48 (s, PCH2CH2CH2CH3), 16.43 and 16.51 (d, 6JPC=6.23 Hz, SiC(CH3)3), 18.08 (s, POCH2CH3), 23.43 (t, 2JPC=3.15 and 3.15 Hz, PCH2CH2CH2CH3), 23.69 and 23.90 (d, 3JPC=15.90 Hz, PCH2CH2CH2CH3), 25.75 (s, SiC(CH3)3), 27.22 and 28.54 (2×d, JPC=99.6 and 99.0 Hz, PCH2CH2CH2CH3), 31.55 and 31.70 (2×d, 3JPC=11.63 and 11.63 Hz, C(4)), 34.54 (t, 2JPC=8.25 and 8.55 Hz, C(5)), 60.15 (2×d, 2JPOC=6.30 and 6.83 Hz, POCH2CH3), 77.97 and 78.22 (d, 3JPC=18.45 Hz, C(3)), 136.64 and 138.24 (2×d, JPC=119.78 and 120.08 Hz, C(1)), 148.51 (d, 2JPC=9.38 Hz, C(2)); 31P-NMR (121 MHz, CDCl3) δP 42.77 and 43.15; MS (CI, CH4) m/z 347.2 (16%) (MH+), 215.1 (100), 375.3 (44), 289.2 (39). Synthesis of (±)-cis-ethyl [3(t-butyldimethylsilyloxy)cyclopentanyl]butylphosphinate (9)

Workup

  1. customafter which time the solvent was removed in vacuo
  2. customThe residue was partitioned between DCM (50 cm3) and water (30 cm3)
  3. extractionthe aqueous layer was further extracted with DCM (3×20 cm3)
  4. washThe combined organic layers were washed with water (2×30 cm3) and brine (40 cm3)
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customthe solvent removed under reduced pressure
  8. customThe crude product was purified by short column vacuum chromatography on silica gel (15% ethanol/ethyl acetate)

Sources & evidence

ORD record
ord-e29c8e3ab3824b30b1185bc9dec8b722
Source dataset
uspto-grants-2005_11
Patent number
US06962907B2

Reaction notes

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