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

HRID 879269ノート

反応式

HRID 879269 の反応式
[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]

参加物

8

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 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)phthalazine触媒HCID 962Water溶媒2 回

反応条件

温度
0 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-b119e15b0a6a48178b356afbe37ac2e5
出典データセット
uspto-grants-2015_03
特許番号
US08987250B2

反応ノート

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