tert-Butanol → (S)-1-(2-Bromo-6-methyl-4-nitrophenyl)ethane-1,2-diol

HRID 879269Notes

Reaction equation

HRID 879269 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:11])[C:3]=1C=C.[C:14]([O-:17])([O-])=O.[K+].[K+].CS(N)(=O)=O.[O-]S([O-])=O.[Na+].[Na+].C[C:32]([OH:35])(C)C>O.CC[C@H]1[C@H]2C[C@H]([C@H](OC3C4C(=CC=CC=4)C(O[C@H](C4C=CN=C5C=4C=C(OC)C=C5)[C@@H]4N5C[C@H](CC)[C@@H](CC5)C4)=NN=3)C3C=CN=C4C=3C=C(OC)C=C4)N(CC2)C1>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:11])[C:3]=1[C@H:14]([OH:17])[CH2:32][OH:35]

Participants

8

Reactant 5

HCID 6386tert-ButanolHCID 11430Potassium CarbonateHCID 24437Sodium SulfiteHCID 72879MethanesulfonamideHCID 866997861-Bromo-3-methyl-5-nitro-2-vinylbenzene

Product 1

HCID 70982486(S)-1-(2-Bromo-6-methyl-4-nitrophenyl)ethane-1,2-diolYield 50%

Reagents, catalysts & solvents 2

HCID 510036741-((1R)-((2R,4R,5S)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)-4-((1R)-((2R,4S,5R)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)phthalazineCatalystHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

The reaction mixture of 1-Bromo-3-methyl-5-nitro-2-vinylbenzene (30.0 g, 0.124 mol), AD-mix α (173.5 g: 0.104 g of K2OsO4.2H2O; 1.389 g of (DHQ)2PHAL; 51.038 g of K2CO3 and 120.99 g of K4Fe(CN)6), MeSO2NH2 (11.8 g, 0.124 mol) in t-BuOH (250 mL) and H2O (250 mL) was stirred at 0° C. for 3 days. Na2SO3 (15 g) was added and stirred at room temperature for 40 min to quench the reaction. The reaction mixture was treated with water (1 L) and the resulting mixture was extracted with EtOAc (3×200 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered, concentrated in vacuo, and purified by silica gel column (Petroleum Ether:EtOAc (2:1), isocratic) to afford (S)-1-(2-Bromo-6-methyl-4-nitrophenyl)ethane-1,2-diol (17 g, 50%) as yellow solid. 1H-NMR: 400 MHz, (CDCl3) δ: 8.26 (s, 1H), 7.99 (s, 1H), 5.56-5.54 (m, 1H), 3.94-3.92 (m, 1H), 3.81-3.78 (m, 1H), 2.82 (d, broad, 1H), 2.67 (s, 3H), 2.18-2.15 (m, 1H).

Workup

  1. stirringstirred at room temperature for 40 min
  2. customto quench
  3. customthe reaction
  4. extractionthe resulting mixture was extracted with EtOAc (3×200 mL)
  5. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. custompurified by silica gel column (Petroleum Ether:EtOAc (2:1), isocratic)

Sources & evidence

ORD record
ord-b119e15b0a6a48178b356afbe37ac2e5
Source dataset
uspto-grants-2015_03
Patent number
US08987250B2

Reaction notes

Loading…