Triphenylphosphine → 3-Bromo-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

HRID 2275180Notes

Reaction equation

HRID 2275180 reaction equation
[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[C:7](=[O:22])[C:8]4[CH:20]=[C:19]([OH:21])[CH:18]=[CH:17][C:9]=4[C:10]([CH3:16])([CH3:15])[C:11]=3[NH:12]2)=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:42][C:43]1([CH3:50])[O:47][C@@H:46]([CH2:48]O)[CH2:45][O:44]1.C(OC(N=NC(OC(C)C)=O)=O)(C)C>C(OCC)(=O)C.C1COCC1>[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[C:7](=[O:22])[C:8]4[CH:20]=[C:19]([O:21][CH2:48][C@H:46]5[CH2:45][O:44][C:43]([CH3:50])([CH3:42])[O:47]5)[CH:18]=[CH:17][C:9]=4[C:10]([CH3:16])([CH3:15])[C:11]=3[NH:12]2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 736057(+)-SolketalHCID 668347143-Bromo-9-hydroxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

Product 1

HCID 668343293-Bromo-9-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-oneYield 51%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

Under nitrogen atmosphere, 3-bromo-9-hydroxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one (Compound JJ2, 356 mg, 1.00 mmol) and triphenylphosphine (317 mg, 1.2 eq.) were added with THF (3 ml), followed by dropwise addition of ((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-methanol (148 μl, 1.2 eq.) and diisopropyl azodicarboxylic acid (252 μl, 1.3 eq.). The mixture was then stirred at 50° C. for 2 hr. After cooling, the reaction solution was added with ethyl acetate, washed with brine and dried over magnesium sulfate. After filtration and the concentration under reduced pressure, the resulting residues were purified by silica gel column chromatography (ethyl acetate/dichloromethane) to yield the solid, which was then washed with dichloromethane to obtain the title compound (white powder, 241.6 mg, 51%).

Workup

  1. temperatureAfter cooling
  2. washwashed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationAfter filtration
  5. concentrationthe concentration under reduced pressure
  6. customthe resulting residues were purified by silica gel column chromatography (ethyl acetate/dichloromethane)
  7. customto yield the solid, which
  8. washwas then washed with dichloromethane

Sources & evidence

ORD record
ord-9ca3c767aba649bebd4297f354bff69c
Source dataset
uspto-grants-2015_09
Patent number
US09126931B2

Reaction notes

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