1-Propanol → [(R)-2-Hydroxy-1-(4-methoxy-phenyl)-ethyl]-carbamic acid benzyl ester

HRID 454975

反応式

HRID 454975 の反応式
[CH2:1]([NH:8][C:9](=[O:11])[O-:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].[C:14]([O:18]Cl)(C)(C)C.C=[CH:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.[CH2:28]([OH:31])CC>CCOC(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>[CH2:21]([O:11][C:9](=[O:10])[NH:8][C@H:1]([C:2]1[CH:7]=[CH:6][C:5]([O:18][CH3:14])=[CH:4][CH:3]=1)[CH2:28][OH:31])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

参加物

8

反応物 5

HCID 10311-Propanol3 回HCID 7501StyreneHCID 14798Sodium HydroxideHCID 521297Tert-Butyl hypochloriteHCID 22253685N-benzylcarbamate

生成物 1

HCID 10957582[(R)-2-Hydroxy-1-(4-methoxy-phenyl)-ethyl]-carbamic acid benzyl ester収率 63%

試薬・触媒・溶媒 2

HCID 112172021,4-Bis(dihydroquinidine)phthalazine触媒HCID 8857Ethyl Acetate溶媒

実験手順

To 1.88 g (12.4 mmol) of benzylcarbamate suspended in 16 mL n-propanol was added 12.2 mL 1 N NaOH (12.2 mmol), and freshly prepared tBuOCl (1.4 mL, 12.2 mmol) and then stirred for 8 min at rt. It was then cooled to 0° C. followed by the addition of the catalyst (DHQD)2PHAL (156 mg, 0.2 mmol) dissolved in 14 mL n-PrOH. This was followed by the addition of the styrene (538 uL, 4 mmol) also dissolved in 20 mL n-PrOH, and stirred for another 8 min. Then K2OsO4.2H2O (58.8 mg, 0.16 mmol) was added directly, and the resulting mixture stirred for 1.5 hr at 0° C. Several color changes were observed, from brown, to bright red, to orange and then finally light yellow. Dilute with EtOAc, and quench with aq. Na2S2O3. The organic layer was separated and the aqueous layer extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, and concentrated. It was purified by flash column 20-40% EtOAc/hexanes to obtain 761 mg (63%) of the product.

後処理

  1. temperatureIt was then cooled to 0° C.
  2. stirringstirred for another 8 min
  3. stirringthe resulting mixture stirred for 1.5 hr at 0° C
  4. customquench with aq. Na2S2O3
  5. customThe organic layer was separated
  6. extractionthe aqueous layer extracted with EtOAc
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customIt was purified by flash column 20-40% EtOAc/hexanes

出典と根拠

ORDレコード
ord-ec0a27f3e30e46ecae5db030171e3e1b
出典データセット
uspto-grants-2013_07
特許番号
US08497271B2

関連ノート

読み込み中…