Dichloromethane → (2R)-Methyl 2-((tert-butoxycarbonyl)amino)-3-((tetrahydro-2H-pyran-2-yl)oxy)propanoate

HRID 524356

反応式

HRID 524356 の反応式
C(Cl)Cl.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.[CH3:21][O:22][C:23](=[O:35])[C@@H:24]([CH2:33][OH:34])[NH:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27].[O:36]1[CH:41]=[CH:40][CH2:39][CH2:38][CH2:37]1>C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C(OCC)(=O)C>[C:29]([O:28][C:26]([NH:25][C@H:24]([CH2:33][O:34][CH:37]1[CH2:38][CH2:39][CH2:40][CH2:41][O:36]1)[C:23]([O:22][CH3:21])=[O:35])=[O:27])([CH3:32])([CH3:30])[CH3:31]

参加物

7

反応物 4

HCID 6344DichloromethaneHCID 80803,4-dihydro-2H-pyranHCID 377723N-Boc-D-serine methyl esterHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)

生成物 1

HCID 13969838(2R)-Methyl 2-((tert-butoxycarbonyl)amino)-3-((tetrahydro-2H-pyran-2-yl)oxy)propanoate収率 96%

試薬・触媒・溶媒 2

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)触媒HCID 8857Ethyl Acetate溶媒

実験手順

To a 2 L three neck flask fitted with a magnetic stirbar, under argon, was added CH2Cl2 (500 mL), PPTs (pyridinium-p-toluene sulfonate) (2 g, 0.008 mol). After dissolving the PPTs by stirring, N-(tert-butoxycarbonyl)-D-serine methyl ester 1 (97.9 g, 0.446 mol) was added to give a clear yellow solution. DHP (3,4-dihydro-2H-pyran) (105 mL, 1.16 mol) was added in one portion. The clear yellow solution was stirred at room temperature over 60 hr to give a slightly cloudy yellow mixture. The mixture was evaporated to give an off-white solid. Ethyl acetate (650 mL) was added to the residue and stirred for 20 minutes to dissolve. The solution was washed with 1.2M HCl (1×500 mL) to pH 4, sat. NaHCO3 (1×600 mL plus 1λ300 mL) to pH 7, brine (1×500 mL), dried over MgSO4 (20 g), filtered and concentrated under reduced pressure to give 129 g (96%) of product 2 as a waxy white solid. 1H NMR (60 MHz, CDCl3) δ 5.2-5.7 (br m, 1H), 3.4-4.8 (m, 9H), 1.4-1.8 (m, 15H).

後処理

  1. customto give a clear yellow solution
  2. stirringThe clear yellow solution was stirred at room temperature over 60 hr
  3. customto give a slightly cloudy yellow mixture
  4. customThe mixture was evaporated
  5. customto give an off-white solid
  6. stirringstirred for 20 minutes
  7. dissolutionto dissolve
  8. washThe solution was washed with 1.2M HCl (1×500 mL) to pH 4, sat. NaHCO3 (1×600 mL plus 1λ300 mL) to pH 7, brine (1×500 mL)
  9. dry with materialdried over MgSO4 (20 g)
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-7c5585eb0a4748d1814f10af34088818
出典データセット
uspto-grants-2016_05
特許番号
US09340534B2

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