Tributyltin Chloride → 4-(2-Tetrahydropyranyloxy)-1-tributylstannyl-1-butyne

HRID 613383Notes

Reaction equation

HRID 613383 reaction equation
C([Li])CCC.[CH2:6]([O:10][CH:11]1[CH2:16][CH2:15][CH2:14][CH2:13][O:12]1)[CH2:7][C:8]#[CH:9].[CH2:17]([Sn:21](Cl)([CH2:26][CH2:27][CH2:28][CH3:29])[CH2:22][CH2:23][CH2:24][CH3:25])[CH2:18][CH2:19][CH3:20]>C1COCC1>[O:12]1[CH2:13][CH2:14][CH2:15][CH2:16][CH:11]1[O:10][CH2:6][CH2:7][C:8]#[C:9][Sn:21]([CH2:22][CH2:23][CH2:24][CH3:25])([CH2:26][CH2:27][CH2:28][CH3:29])[CH2:17][CH2:18][CH2:19][CH3:20]

Participants

5

Reactant 3

HCID 15096Tributyltin ChlorideHCID 1424402-(3-Butynyloxy)tetrahydro-2H-pyranHCID 178418339Butyllithium

Product 1

HCID 111022914-(2-Tetrahydropyranyloxy)-1-tributylstannyl-1-butyneYield 27%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of n-butyllithium in hexanes (1.6 M, 18.8 mL, 30 mmole) was added in a stream over 2 min to a solution of 2-(3-butynyloxy)tetrahydro-2H-pyran (4.7 mL, 30 mmole) in dry THF (60 mL) at 0° C. under argon. After 0.5 hr, tributyltin chloride (8.1 mL, 30 mmole) was added all at once, and the reaction was warmed to RT. After 3 hr, the reaction was diluted with hexanes (300 mL) and washed sequentially with H2O (2×60 mL), 10% KF (2×30 mL), and saturated brine (60 mL). Drying (Na2SO4), concentration, and silica gel chromatography (3% EtOAc/hexanes) gave the title compound (3.58 g, 27%) as a nearly colorless oil: TLC (5% EtOAc/hexanes) Rf 0.37; 1H NMR (400 MHz, CDCl3) δ 4.66 (narrow t, 1 H), 3.75-3.96 (m, 2 H), 3.49-3.62 (m, 2 H), 2.56 (app t, 2 H), 1.76-1.91 (m, 1 H), 1.65-1.78 (m, 1H), 1.42-1.65 (m, 10 H), 1.22-1.41 (m, 6 H), 0.82-1.08 (m, 15 H).

Workup

  1. waitAfter 3 hr
  2. washwashed sequentially with H2O (2×60 mL), 10% KF (2×30 mL), and saturated brine (60 mL)
  3. customDrying
  4. concentration(Na2SO4), concentration, and silica gel chromatography (3% EtOAc/hexanes)

Sources & evidence

ORD record
ord-eb279bb3e06b4aca977ef02d96171d32
Source dataset
uspto-grants-1999_12
Patent number
US06008213

Reaction notes

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