Triisopropyl borate → HCID 66780814, compound

HRID 572956Notes

Reaction equation

HRID 572956 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([O:37][CH:38]2[CH2:43][CH2:42][CH2:41][CH2:40][O:39]2)=[C:6]([N:8]2[C:20]3[CH:19]=[CH:18][C:17]([C:21]([CH3:28])([CH2:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH3:22])=[CH:16][C:15]=3[C:14]3[C:9]2=[CH:10][CH:11]=[C:12]([C:29]([CH3:36])([CH2:31][C:32]([CH3:35])([CH3:34])[CH3:33])[CH3:30])[CH:13]=3)[CH:7]=1.[Li]CCCC.C([O:52][B:53](OC(C)C)[O:54]C(C)C)(C)C>C1COCC1.CCCCCC>[CH3:28][C:21]([C:17]1[CH:18]=[CH:19][C:20]2[N:8]([C:6]3[C:5]([O:37][CH:38]4[CH2:43][CH2:42][CH2:41][CH2:40][O:39]4)=[C:4]([B:53]([OH:54])[OH:52])[CH:3]=[C:2]([CH3:1])[CH:7]=3)[C:9]3[C:14]([C:15]=2[CH:16]=1)=[CH:13][C:12]([C:29]([CH3:30])([CH2:31][C:32]([CH3:33])([CH3:35])[CH3:34])[CH3:36])=[CH:11][CH:10]=3)([CH2:23][C:24]([CH3:25])([CH3:26])[CH3:27])[CH3:22]

Participants

6

Reactant 3

HCID 21531Triisopropyl borateHCID 66779857HCID 66779857, compoundHCID 178418339Butyllithium

Product 1

HCID 66780814HCID 66780814, compoundYield 78.1%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

The 9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-3,6-bis(2,4,4-trimethylpentan-2-yl)-9H-carbazole (5.00 g, 8.6 mmol) is dissolved in 50 mL THF in a 250 mL round bottom flask in an ice water bath. n-BuLi (7.0 ml of a 1.6 M solution in hexane, 11.2 mmol) is added dropwise via syringe (soln turns yellow in color) and the brown solution stirred for 3 hours. Triisopropylborate (2.37 mL, 11.2 mmol) is added dropwise via syringe and the solution stirred for one hour, during which time the mixture became turbid and darkened in color. The mixture is quenched with 100 mL ice water. The solution is extracted with 2×100 mL Et2O. The combined organic portions are dried with MgSO4, filtered and rotovapped down to a white solid (5.1 g). This solid is added to 200 mL water and stirred for 1.5 hrs. The mixture is extracted with 150 and 100 mL Et2O. The combined organic extract is dried with MgSO4, filtered and rotovapped down to yield 4.2 g (78% yield) of a white powder. 1H NMR (CDCl3): δ 8.07 (d, JH—H=1.4 Hz, 1H, CBZ), 8.04 (d, JH—H=1.4 Hz, 1H, CBZ), 7.69 (d, JH—H=2.3 Hz, 1H, aryl), 7.42 (dd, JH—H=8.6, 1.8 Hz, 2H, CBZ), 7.40 (dd, JH—H=8.6, 1.7 Hz, 1H, CBZ), 7.37 (d, JH—H=2.3 Hz, 1H, aryl), 7.18 (d, JH—H=8.6 Hz, 1H, CBZ), 6.99 (d, JH—H=8.6 Hz, 1H, CBZ), 6.34 (s, 2H, OH), 3.80 (m, 2H, THP), 2.91 (m, 1H, THP), 2.39 (s, 3H, aryl Me), 1.89 (dd, JH—H=12.8, 4.2 Hz, 2H, tOCT CH2), 1.82 (d, JH—H=14.5 Hz, 2H, tOCT CH2), 1.55 (s, 3H, tOCT CMe2), 1.52 (s, 3H, tOCT CMe2), 1.48 (s, 3H, tOCT CMe2), 1.45 (s, 3H, tOCT CMe2), 0.71 (s, 9H, tOCT tBu), 0.70 (s, 9H, tOCT tBu).

Workup

  1. stirringthe solution stirred for one hour, during which time the mixture
  2. customThe mixture is quenched with 100 mL ice water
  3. extractionThe solution is extracted with 2×100 mL Et2O
  4. dry with materialThe combined organic portions are dried with MgSO4
  5. filtrationfiltered
  6. additionThis solid is added to 200 mL water
  7. stirringstirred for 1.5 hrs
  8. extractionThe mixture is extracted with 150 and 100 mL Et2O
  9. extractionThe combined organic extract
  10. dry with materialis dried with MgSO4
  11. filtrationfiltered

Sources & evidence

ORD record
ord-4ddc09d9f8b44ca58e09bdf63019414d
Source dataset
uspto-grants-2015_05
Patent number
US09029487B2

Reaction notes

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