Triisopropyl borate → HCID 67209101, compound

HRID 508667Notes

Reaction equation

HRID 508667 reaction equation
[C:1]12([C:11]3[C:12]([O:19][CH2:20][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)=[CH:13][C:14]([CH3:18])=[C:15](Br)[CH:16]=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.C(=O)=O.CC(C)=O.[Li]CCCC.C([O:42][B:43](OC(C)C)[O:44]C(C)C)(C)C>C1COCC1.CCCCCC>[C:1]12([C:11]3[C:12]([O:19][CH2:20][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)=[CH:13][C:14]([CH3:18])=[C:15]([B:43]([OH:44])[OH:42])[CH:16]=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2

Participants

7

Reactant 4

HCID 21531Triisopropyl borateHCID 18522661Acetone cardiceHCID 67209107HCID 67209107, compoundHCID 178418339Butyllithium

Product 1

HCID 67209101HCID 67209101, compoundYield 60.4%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 5-(1-adamantyl)-4-benzyloxy-2-methylphenyl bromide (2.66 g, 6.47 mmol) in THF (10 mL) at −78° C. (dry ice/acetone bath) under argon was added 1.6 M n-BuLi (11.64 mmol) in hexane (7.3 mL) in one portion. This mixture was stirred at −78° C. for 15 min. Tri(isopropyl)borate (4.5 mL, 19.40 mmol) was added, and the resulting solution was stirred at −78° C. for 20 min before being allowed to warm to room temperature with stirring overnight. The reaction mixture was quenched with 1 N HCl (40 mL) and then extracted with EtOAc (100 and 60 mL). The combined organic extracts were washed with brine and dried. Solvents were removed at reduced pressure, and the residue was washed with hexane to give 1.47 g (60%) of 5-(1-adamantyl)-4-benzyloxy-2-methylphenylboronic acid as a white solid, mp 243-247° C. IR 3226, 2903, 2848, 1328 cm−1; 1H NMR (CDCl3) δ 1.74 (bs, 6H, AdCH2), 2.05 (bs, 3H, AdCH), 2.20 (bs, 6H, AdCH2), 2.82 (s, 3H, CH3), 5.19 (s, 2H, C6H5CH2), 6.85 (s, 1H, 3-ArH), 7.31-7.54 (m, 5H, C6H5), 8.19 ppm (s, 1H, 6-ArH).

Workup

  1. stirringthe resulting solution was stirred at −78° C. for 20 min
  2. temperatureto warm to room temperature
  3. stirringwith stirring overnight
  4. customThe reaction mixture was quenched with 1 N HCl (40 mL)
  5. extractionextracted with EtOAc (100 and 60 mL)
  6. washThe combined organic extracts were washed with brine
  7. customdried
  8. customSolvents were removed at reduced pressure
  9. washthe residue was washed with hexane

Sources & evidence

ORD record
ord-86b100e9c5b145aa8a7d32aa5a68b13b
Source dataset
uspto-grants-2015_08
Patent number
US09096544B2

Reaction notes

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