Trimethylsilylacetylene → 4-Hydroxy-4-trimethylsilanylethynyl-tetrahydro-pyran-2-carboxylic Acid Ethyl Ester

HRID 1264041Notes

Reaction equation

HRID 1264041 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[Li]CCCC.[CH2:12]([O:14][C:15]([CH:17]1[CH2:22][C:21](=[O:23])[CH2:20][CH2:19][O:18]1)=[O:16])[CH3:13]>C1COCC1>[CH2:12]([O:14][C:15]([CH:17]1[CH2:22][C:21]([OH:23])([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH2:20][CH2:19][O:18]1)=[O:16])[CH3:13]

Participants

5

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 54067561Ethyl tetrahydro-4-oxo-2H-pyran-2-carboxylateHCID 178418339Butyllithium

Product 1

HCID 536671564-Hydroxy-4-trimethylsilanylethynyl-tetrahydro-pyran-2-carboxylic Acid Ethyl EsterYield 61%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A cold (−78° C.), stirred solution of (trimethylsilyl)acetylene (1.80 g, 18.24 mmol) in anhydrous THF (30 mL) was treated with nBuLi (7.3 mL in hexane, 18.24 mmol) under nitrogen. The colorless solution was stirred for 30 minutes and followed by the addition of 4-oxo-tetrahydro-pyran-2-carboxylic acid ethyl ester (2.62 g, 15.2 mmol) in anhydrous THF (30 mL). The reaction was warmed up to room temperature, stirred for 2 hours, and quenched with water (30 mL). After removal of THF, the product was extracted with EtOAc (2×60 mL). The combined organic layer was washed with brine, dried over sodium sulfate, and concentrated to give 2.50 g (61%) of yellow oil: 1H NMR (CDCl3) δ 0.17 (s, 9H), 1.30 (t, 3H), 1.76-1.90 (m, 3H), 2.25 (m, 1H), 3.66 (tt, 1H), 4.11-4.21 (m, 2H), 4.24 (q, 2H).

Workup

  1. stirringstirred for 2 hours
  2. customquenched with water (30 mL)
  3. customAfter removal of THF
  4. extractionthe product was extracted with EtOAc (2×60 mL)
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-a97ea2a426844024978c0c0f40dd5142
Source dataset
uspto-grants-2003_04
Patent number
US06541481B2

Reaction notes

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