(6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilane → 2-{5'-[6-(tert-Butyl-dimethyl-silanyloxy)-hexyl]-[2,2']bithiophenyl-5-yl}-4,4,5,5-tetramethyl-[1,3,2}dioxaborolane

HRID 351302Notes

Reaction equation

HRID 351302 reaction equation
[S:1]1[C:5]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14])=[CH:4][CH:3]=[C:2]1[C:20]1[S:21][CH:22]=[CH:23][CH:24]=1.C([Li])CCC.[BH:30]([OH:32])[OH:31].O[C:34]([C:37](O)([CH3:39])[CH3:38])([CH3:36])[CH3:35]>C1COCC1>[C:16]([Si:13]([CH3:14])([CH3:15])[O:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][C:5]1[S:1][C:2]([C:20]2[S:21][C:22]([B:30]3[O:32][C:37]([CH3:39])([CH3:38])[C:34]([CH3:36])([CH3:35])[O:31]3)=[CH:23][CH:24]=2)=[CH:3][CH:4]=1)([CH3:18])([CH3:19])[CH3:17]

Participants

5

Reactant 3

HCID 58807316(6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilaneHCID 178418339ButyllithiumHCID 178459139HCID 178459139, compound

Product 1

HCID 588073092-{5'-[6-(tert-Butyl-dimethyl-silanyloxy)-hexyl]-[2,2']bithiophenyl-5-yl}-4,4,5,5-tetramethyl-[1,3,2}dioxaborolaneYield 95.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To an ice-cooled solution of (6-[2,2′]bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilane (10 g, 19.76 mmol) in anhydrous THF (150 ml) was added dropwise a solution of n-butyllithium (2.5 M in hexanes, 7.91 ml, 19.76 mmol) under nitrogen, with stirring. After 2 h, pinacol boronate (4.04 g, 21.72 mmol) was added. The ice bath was removed, and the resultant mixture was stirred overnight at room temperature. The reaction was quenched with the addition of saturated aqueous NH4Cl and the mixture extracted with ethyl acetate (3×70 ml). The combined organic extracts were washed with brine, dried over magnesium sulphate, and evaporated under reduced pressure. The residue was purified by column chromatography on silica, eluting with petroleum ether/ethyl (9:1), to give the product as a blue oil (9.52 g, 72%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.46 (d, J=3.6 Hz, 1 H, Ar—H), 7.10 (d, J=3.6 Hz, 1H, Ar—H), 6.99 (d, J=3.4 Hz, 1H, Ar—H), 6.62 (d, J=3.4 Hz, 1H, Ar—H), 3.56 (t, J=6.4 Hz, 2H, OCH2), 2.73 (t, J=7.4 Hz, 2H, ArCH2), 1.21–1.70 (m, 20H, CH2 and CH3), 0.86 (s, 9H, CH3), 0.01 (s, 6H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 145.9 (2×quat.), 144.8 (quat.), 138.0 (CH.), 134.7 (quat.), 125.0 (CH), 124.2 (CH); 124.1 (CH), 84.1 (quat.), 63.2 (OCH2), 32.8 (CH2), 31.6 (CH2), 30.2 (CH2), 28.9 (CH2), 26.0 (CH3) 25.6 (CH2), 24.8 (CH3),18.4 (quat.), −5.2 (CH3); MS (m/e): 506 (M+, 32%), 331 (31), 305 (31), 279 (100), 261 (32), 205 (51), 83 (71).

Workup

  1. customThe ice bath was removed
  2. stirringthe resultant mixture was stirred overnight at room temperature
  3. customThe reaction was quenched with the addition of saturated aqueous NH4Cl
  4. extractionthe mixture extracted with ethyl acetate (3×70 ml)
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over magnesium sulphate
  7. customevaporated under reduced pressure
  8. customThe residue was purified by column chromatography on silica
  9. washeluting with petroleum ether/ethyl (9:1)

Sources & evidence

ORD record
ord-8152df6379bc46debdc8832e51c1f05d
Source dataset
uspto-grants-2007_02
Patent number
US07183418B2

Reaction notes

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