Dimethylformamide → (S)-ethyl 2-tert-butoxy-2-(6-cyano-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

HRID 926144ノート

反応式

HRID 926144 の反応式
[C:1]([O:5][C@@H:6]([C:12]1[C:21]([CH3:22])=[CH:20][C:19]2[C:14](=[CH:15][CH:16]=[C:17](Cl)[CH:18]=2)[C:13]=1[O:24][S:25]([C:28]([F:31])([F:30])[F:29])(=[O:27])=[O:26])[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2].C(=O)(O)[O-].[Na+].[CH3:37][N:38](C=O)C>[C-]#N.[Zn+2].[C-]#N.CC(C1C=C(C(C)C)C(C2C(P(C3CCCCC3)C3CCCCC3)=CC=CC=2)=C(C(C)C)C=1)C.C1C=[C-]C(CCN)=CC=1.Cl[Pd+]>[C:1]([O:5][C@@H:6]([C:12]1[C:21]([CH3:22])=[CH:20][C:19]2[C:14](=[CH:15][CH:16]=[C:17]([C:37]#[N:38])[CH:18]=2)[C:13]=1[O:24][S:25]([C:28]([F:31])([F:30])[F:29])(=[O:27])=[O:26])[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2]

参加物

6

反応物 3

HCID 6228DimethylformamideHCID 516892Sodium BicarbonateHCID 89681783(S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

生成物 1

HCID 131735014(S)-ethyl 2-tert-butoxy-2-(6-cyano-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

試薬・触媒・溶媒 2

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 54751079XPhos Palladacycle触媒

反応条件

温度
110 °C

実験手順

A mixture of (S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate (0.546 g, 1.13 mmol), zinc(II) cyanide (0.080 g, 0.678 mmol), XPhos Palladacycle (Strem, 0.083 g, 0.113 mmol) and sodium bicarbonate (0.009 g, 0.113 mmol) in DMF (3.0 mL) was sparged with nitrogen for 5 minutes. The reaction mixture was heated in microwave at 110° C. for 1 hour. The reaction mixture was diluted with ethyl acetate and washed with 5% lithium chloride solution (2×), brine and dried (MgSO4) and filtered. Concentration and purification by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes) gave the title compound. NMR (400 MHz, CDCl3) δ 8.19 (s, H), 8.13 (d, J=8.8 Hz, H), 7.74 (s, H), 7.71 (d, J=8.8 Hz, H), 5.73 (s, H), 4.27-4.09 (m, 2H), 2.59 (s, 3H), 1.21 (s, 9H), 1.17 (t, J=7.1 Hz, 2H).

後処理

  1. customwas sparged with nitrogen for 5 minutes
  2. additionThe reaction mixture was diluted with ethyl acetate
  3. washwashed with 5% lithium chloride solution (2×), brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationConcentration and purification by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-4ffe05183e484b268034dad5f785f50b
出典データセット
uspto-grants-2016_03
特許番号
US09284323B2

反応ノート

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