Triisopropyl borate → HCID 67209066, compound

HRID 508674Notes

Reaction equation

HRID 508674 reaction equation
[C:1]12([C:11]3[CH:12]=[C:13](Br)[CH:14]=[C:15]([O:25][CH3:26])[C:16]=3[O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=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.[B:40](OC(C)C)([O:45]C(C)C)[O:41]C(C)C>C1COCC1.CCCCCC>[C:1]12([C:11]3[CH:12]=[C:13]([B:40]([OH:45])[OH:41])[CH:14]=[C:15]([O:25][CH3:26])[C:16]=3[O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=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 67209097HCID 67209097, compoundHCID 178418339Butyllithium

Product 1

HCID 67209066HCID 67209066, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 3-(1-adamantyl)-4-benzyloxy-5-methoxyphenyl bromide (2.85 g, 6.67 mmol) in THF (12 mL) at −78° C. (dry ice/acetone bath) under argon was added 1.6 M n-BuLi (10.7 mmol) in hexane (6.67 mL) in one portion. This mixture was stirred at −78° C. for 15 min. Tri(isopropyl) borate (4.60 mL, 20.0 mmol) was added next, and the resulting solution was stirred at −78° C. for 20 min before being allowed to warm to room temperature with stirring overnight. The 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 and dried to give 2.3 g (88%) of 3-(1-adamantyl)-4-benzyloxy-5-methoxyphenylboronic acid as a cream solid, mp 148-151° C. IR 3219, 2903, 2848, 1410, 1340, 1201 cm−1; 1H NMR (CDCl3) δ 1.72 (bs, 6H, AdCH2), 2.03 (bs, 3H, AdCH), 2.17 (m, 6H, AdCH2), 3.99 (s, 3H, OCH3), 5.21 (s, 2H, C6H5CH2), 7.31-7.58 (m, 5H, C6H5), 7.68 (d, J=1.4 Hz, 1H, 6-ArH), 7.92 ppm (d, J=1.4 Hz, 1H, 2-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 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
  10. customdried

Sources & evidence

ORD record
ord-2df8a3368a6c408d8e2554be2aafc2dd
Source dataset
uspto-grants-2015_08
Patent number
US09096544B2

Reaction notes

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