Lithium hydroxide, monohydrate → HCID 67085566, compound

HRID 2036760Notes

Reaction equation

HRID 2036760 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:8]2[N:7]([C@@H]3C[C@H](C)CC[C@H]3C(C)C)[C:6]3[CH2:21][CH:22]4[NH:26][CH:25]([C:5]=3[C:4]=2[C:3]=1[C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:24][CH2:23]4.O.[OH-].[Li+]>O1CCCC1.CO.O>[Br:1][C:2]1[CH:10]=[CH:9][C:8]2[NH:7][C:6]3[CH2:21][CH:22]4[NH:26][CH:25]([C:5]=3[C:4]=2[C:3]=1[C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:24][CH2:23]4

Participants

6

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 67173087HCID 67173087, compound

Product 1

HCID 67085566HCID 67085566, compoundYield 92.1%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of the product from step E (8.51 g, 15.23 mmol) in tetrahydrofuran (102 mL) and MeOH (51 mL) was added a solution of lithium hydroxide monohydrate (1.92 g, 45.69 mmol) in water (25 mL) at ambient temperature. The mixture was stirred vigorously for 2.5 h, quenched with aqueous saturated NH4Cl solution (75 mL), and extracted with ethyl acetate (2×200 mL). The combined extracts were dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography (SiO2, hexane/ethyl acetate, 70:30) to afford (+)-tert-butyl 2-bromo-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate (5.29 g, 92%) as a white solid: [α]D=+142.4° (c 0.33, MeOH); 1H NMR (CDCl3, 300 MHz) δ 7.93 (s, 1H), 7.61 (d, J=0.9 Hz, 1H), 7.11-7.23 (dd, J=16.8, 8.4 Hz, 2H), 5.14 (s, 1H), 4.65 (s, 1H), 3.28-3.57 (m, 1H), 2.47 (d, J=16.2 Hz, 1H), 2.10-2.38 (m, 2H), 1.88-1.98 (m, 1H), 1.54-1.70 (m, 1H), 1.38 (s, 9H).

Workup

  1. customquenched with aqueous saturated NH4Cl solution (75 mL)
  2. extractionextracted with ethyl acetate (2×200 mL)
  3. dry with materialThe combined extracts were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by column chromatography (SiO2, hexane/ethyl acetate, 70:30)

Sources & evidence

ORD record
ord-a41dfb507c1849df8f6fd0a87dcc1a18
Source dataset
uspto-grants-2013_11
Patent number
US08575186B2

Reaction notes

Loading…