Tributyltin Chloride → 2,5-Dimethoxy-3-(2-tributylstannylethynyl)-tetrahydrofuran

HRID 2299941Notes

Reaction equation

HRID 2299941 reaction equation
Br[C:2](Br)=[CH:3][CH:4]1[CH2:8][CH:7]([O:9][CH3:10])[O:6][CH:5]1[O:11][CH3:12].C([Li])CCC.[CH2:19]([Sn:23](Cl)([CH2:28][CH2:29][CH2:30][CH3:31])[CH2:24][CH2:25][CH2:26][CH3:27])[CH2:20][CH2:21][CH3:22].[NH4+].[Cl-]>CCOCC>[CH3:12][O:11][CH:5]1[CH:4]([C:3]#[C:2][Sn:23]([CH2:24][CH2:25][CH2:26][CH3:27])([CH2:28][CH2:29][CH2:30][CH3:31])[CH2:19][CH2:20][CH2:21][CH3:22])[CH2:8][CH:7]([O:9][CH3:10])[O:6]1

Participants

6

Reactant 4

HCID 15096Tributyltin ChlorideHCID 25517Ammonium ChlorideHCID 183804243-(2,2-Dibromoethenyl)-2,5-dimethoxytetrahydrofuranHCID 178418339Butyllithium

Product 1

HCID 183804392,5-Dimethoxy-3-(2-tributylstannylethynyl)-tetrahydrofuranYield 77%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To solution of crude 3-(2,2-dibromoethenyl)-2,5-dimethoxy-tetrahydrofuran (1.78 g, 5.64 mmol) in ether (30 mL) at −78° C. was added n-butyllithium (9.02 mL of 1.25 M in hex). After 1 hour at −78° C., tributyltin chloride (1.68 mL, 6.20 mmol) was added, and the mixture was allowed to warm to ambient temperature. After 16 hours, ether (35 mL) and saturated aqueous NH4Cl (30 mL) were added. The organic layer was separated, washed with saturated aqueous NH4Cl (30 mL), H2O (25 mL), and saturated aqueous NaHCO3 (25 mL), dried over K2CO3, and evaporated to give an orange oil, which was purified via flash column chromatography with 2% MTBE/hex to furnish 1.92 g (77%) of 2,5-dimethoxy-3-(2-tributylstannylethynyl)-tetrahydrofuran as a colorless oil. A mixture of diastereomers was evident in the 1H NMR spectrum, which was used immediately without further purification. IR: 2923, 1456, 1374, 1215, 1105, 1017, 967 cm−1. Anal. Calculated for C20H38O3Sn: C, 53.96; H, 8.60. Found: C, 54.21; H, 8.66.

Workup

  1. waitAfter 16 hours
  2. customThe organic layer was separated
  3. washwashed with saturated aqueous NH4Cl (30 mL), H2O (25 mL), and saturated aqueous NaHCO3 (25 mL)
  4. dry with materialdried over K2CO3
  5. customevaporated
  6. customto give an orange oil, which
  7. customwas purified via flash column chromatography with 2% MTBE/hex

Sources & evidence

ORD record
ord-75a1cfb2e8ff4ac9b377e9a5c8b5086e
Source dataset
uspto-grants-2002_12
Patent number
US06495699B2

Reaction notes

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