Sodium hydride → rac-ethyl (1R,2R)-2-(4-aminophenyl)cyclopropane-1-carboxylate

HRID 2174211ノート

反応式

HRID 2174211 の反応式
[H-].[Na+].[I-].[CH3:4][S+](C)(C)=O.[NH2:9][C:10]1[CH:15]=[CH:14][C:13](/[CH:16]=[CH:17]/[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:12][CH:11]=1>CS(C)=O>[NH2:9][C:10]1[CH:11]=[CH:12][C:13]([C@@H:16]2[CH2:4][C@H:17]2[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:14][CH:15]=1

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 736317Ethyl 4-aminocinnamate

生成物 1

HCID 68767952rac-ethyl (1R,2R)-2-(4-aminophenyl)cyclopropane-1-carboxylate

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒2 回

実験手順

To a suspension of sodium hydride (36 mg, 0.89 mmol) in DMSO (2 mL) was added the solid trimethyl sulfoxonium iodide (185 mg, 1.05 mmol). The mixture was stirred for 25 min before a solution of ethyl (E)-3-(4-aminophenyl)prop-2-enoate (100 mg, 0.52 mmol) in DMSO (2 mL) was added quickly at RT. The mixture was left to stir overnight. The bulk mixture was quenched with NH4Cl (sat.) and the mixture diluted with water and EtOAc. The layers were separated and the aqueous layer extracted into EtOAc (3×30 mL). The organic fractions were combined, dried with brine then MgSO4 and the solvent removed. Flash chromatography on silica gel, eluting with 20-50% ethyl acetate gradient in n-heptane, gave ethyl (1R,2R)-2-(4-aminophenyl)cyclopropanecarboxylate, 70 mg. 1H NMR (400 MHz, CDCl3) δ 6.96-6.89 (m, 2H), 6.68-6.61 (m, 2H), 4.17 (q, J=7.1 Hz, 2H), 2.44 (ddd, J=9.2, 6.6, 4.2 Hz, 1H), 1.80 (ddd, J=8.4, 5.2, 4.2 Hz, 1H), 1.53 (ddd, J=9.2, 5.2, 4.5 Hz, 1H), 1.28 (t, J=7.1 Hz, 3H), 1.24 (ddd, J=8.3, 6.6, 4.5 Hz, 1H).

後処理

  1. additionwas added quickly at RT
  2. waitThe mixture was left
  3. customThe bulk mixture was quenched with NH4Cl (sat.)
  4. additionthe mixture diluted with water and EtOAc
  5. customThe layers were separated
  6. extractionthe aqueous layer extracted into EtOAc (3×30 mL)
  7. dry with materialdried with brine
  8. customMgSO4 and the solvent removed
  9. washFlash chromatography on silica gel, eluting with 20-50% ethyl acetate gradient in n-heptane

出典と根拠

ORDレコード
ord-e5828ed443d141db9fd38cdc33533811
出典データセット
uspto-grants-2015_06
特許番号
US09060515B2

反応ノート

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