Triethylamine → HCID 178460556, compound

HRID 1062535Notes

Reaction equation

HRID 1062535 reaction equation
[OH:1][CH:2]1[CH2:6][CH2:5][C:4]([CH2:7][PH:8](=[O:13])[O:9][CH:10]([CH3:12])[CH3:11])=[CH:3]1.[Si:14](Cl)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15].C(N(CC)CC)C>CN(C=O)C.CN(C1C=CN=CC=1)C>[Si:14]([O:1][CH:2]1[CH2:6][CH2:5][C:4]([CH2:7][PH:8](=[O:13])[O:9][CH:10]([CH3:11])[CH3:12])=[CH:3]1)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 28928tert-Butyldimethylsilyl chlorideHCID 178460555HCID 178460555, compound

Product 1

HCID 178460556HCID 178460556, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of isopropyl (3-hydroxycyclopentenyl)methylphosphinate (3) (3.5 g, 17.2 mmol) in anhydrous DMF (60 cm3) was treated with t-butyldimethylsilyl chloride (2.85 g, 18.9 mmol), triethylamine (3.6 g, 34.3 mmol) and DMAP (250 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 Na2SO4, filtered and the solvent removed under reduced pressure. The crude product was purified by short column vacuum chromatography on silica gel (5% ethanol/ethyl acetate) to yield the title compound (4) as a colourless oil (4.62 g, 85%): 1H NMR (300 MHz, CDCl3) δ 0.065 and 0.067 (6H, 2×s), 0.870 and 0.874 (9H, 2×s), 1.22 and 1.24 (3H, 2×d, J=6.3 and 6.3 Hz, OCHCH3), 1.31 and 1.33 (3H, 2×d, J=6.0 and 6.0 Hz, OCHCH3), 1.45 and 1.49 (3H, 2×d, J=14.4 and 14.4 Hz, PCH3), 1.69-1.83 (1H, m, C(5)—H), 2.24-2.46 (2H, m, C(5)—H′ and C(4)—H), 2.54-2.68 (1H, m, C(4)—H′), 4.55 (1H, m, OCHCH3), 4.95 (1H, m, C(3)—H), 6.46 (1H, m, C(2)—H), 13 C NMR (75.46 MHz, CDCl3) δ −4.81 and −4.75 (Si(CH3)2, 2×s), 14.0 and 14.19 (PCH3, d, JPC=101.3 and 101.8 Hz), 18.07 and 18.10 (SiC(CH3)3, 2×s), 23.90 and 23.96 (POCCH3, 2×d, 3JPOCC=4.8 Hz), 24.43 (POCCH3, overlapping d, 3JPOCC=3.3 Hz), 25.76 (SiC(CH3)3, br. s), 31.34 (C(4), d, 3JPC=11.5 Hz), 34.42 and 34.55 (C(5), 2×d, 2JPC=9.5 Hz), 68.95 and 68.99 (POCHCH3, d, 2JPOC=6.5 and 5.9 Hz), 77.98 and 78.24 (C(3), d, 3JPC=6.9 and 6.7 Hz), 137.78 and 138.08 (C(2), d, JPC=125.0 and 125.6 Hz), 147.2 (C(1), d, J=10.7 Hz), 31P NMR (121 MHz, CDCl3) δ 38.1, 38.5, (ESI) 319.1869 (MH+-C15H32O3PSi requires 319.1858).

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 Na2SO4
  6. filtrationfiltered
  7. customthe solvent removed under reduced pressure
  8. customThe crude product was purified by short column vacuum chromatography on silica gel (5% ethanol/ethyl acetate)

Sources & evidence

ORD record
ord-c134651e1d0c48b792edca0c91de42ac
Source dataset
uspto-grants-2005_11
Patent number
US06962907B2

Reaction notes

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