2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → HCID 59207331, compound

HRID 644116Notes

Reaction equation

HRID 644116 reaction equation
[S:1]1[C:5]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][CH2:13][C:14]2([CH2:18][CH3:19])[CH2:17][O:16][CH2:15]2)=[CH:4][CH:3]=[C:2]1[C:20]1[S:21][CH:22]=[CH:23][CH:24]=1.C([Li])CCC.C(O[B:34]1[O:38][C:37]([CH3:40])([CH3:39])[C:36]([CH3:42])([CH3:41])[O:35]1)(C)C>C1COCC1>[CH2:18]([C:14]1([CH2:13][O:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][C:5]2[S:1][C:2]([C:20]3[S:21][C:22]([B:34]4[O:38][C:37]([CH3:40])([CH3:39])[C:36]([CH3:42])([CH3:41])[O:35]4)=[CH:23][CH:24]=3)=[CH:3][CH:4]=2)[CH2:17][O:16][CH2:15]1)[CH3:19]

Participants

5

Reactant 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 59207314HCID 59207314, compoundHCID 178418339Butyllithium

Product 1

HCID 59207331HCID 59207331, compoundYield 56.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 3-(6-[2,2′]bithiophenyl-5-yl-hexyloxymethyl)-3-ethyl-oxetane (6.0 g, 16.46 mmol) in anhydrous THF (100 ml) was added n-butyllithium (2.5 M in hexanes, 7.0 ml, 17.50 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture was allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.26 g, 17.5 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with sat. aq. NH4Cl, and the reaction mixture was extracted with ethyl acetate (3×100 ml). The combined organic extracts were washed with water, brine, and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9:1 to 4:1), to give 2-{5′-[6-(3-ethyl-oxetan-3-ylmethoxy)hexyl]-[2,2′]bithiophenyl-5-yl}-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane as a blue oil (4.53 g, 56%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.49 (d, J=3.6 Hz, 1H, Ar—H), 7.14 (d, J=3.6 Hz, 1H, Ar—H), 7.03 (d, J=3.6 Hz, 1H, Ar—H), 6.66 (d, J=3.6 Hz, 1H, Ar—H), 4.43 (d, J=5.8 Hz, 2H, OCH2), 4.34 (d, J=5.8 Hz, 2H, OCH2), 3.48 (s, 2H, OCH2), 3.42 (t, J=6.6 Hz, 2H, OCH2), 2.76 (t, J=7.5 Hz, 2H, ArCH2), 1.32-1.75 (m, 22H, CH2 and CH3), 0.86 (t, J=7.5 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 144.8 (quat.), 143.7 (quat.), 137.0 (CH), 133.7 (quat.), 124.0 (CH), 123.1 (CH), 123.0 (CH), 83.1 (quat.), 77.5 (OCH2), 72.4 (OCH2), 70.4 (OCH2), 42.4 (quat.), 31.5 (CH2), 30.5 (CH2), 29.1 (CH2), 28.4 (CH2), 27.8 (CH2) 25.8 (CH2), 24.9 (CH3), 8.3 (CH3); MS (m/e): 490 (M+, 16%) □305 (79), 223 (25), 205 (100).

Workup

  1. additionAfter complete addition
  2. customThe reaction was quenched with sat. aq. NH4Cl
  3. extractionthe reaction mixture was extracted with ethyl acetate (3×100 ml)
  4. washThe combined organic extracts were washed with water, brine
  5. dry with materialdried over sodium sulphate
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purified by column chromatography on silica
  8. washeluting with petroleum ether/ethyl acetate (9:1 to 4:1)

Sources & evidence

ORD record
ord-d51cd78e613f4131902ee6bca0c5f889
Source dataset
uspto-grants-2010_04
Patent number
US07700643B2

Reaction notes

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