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

HRID 510254Notes

Reaction equation

HRID 510254 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-fa90556cdb744214807e18fb0753060a
Source dataset
uspto-grants-2015_08
Patent number
US09096586B2

Reaction notes

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