Ethyl Acetate → (2S,5S)-1-tert-butyl 4-methyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1,4(2H)-dicarboxylate

HRID 627141

反応式

HRID 627141 の反応式
[C:1]([O:5][C:6]([N:8]([C@@H:18]([CH:28]=C)[CH2:19][O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])[CH2:9][CH:10]([OH:17])[C:11](=C)[C:12]([O:14][CH3:15])=[O:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(OCC)(=O)C>C1(C)C=CC=CC=1.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3OC(C)C)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1>[Si:21]([O:20][CH2:19][C@@H:18]1[CH:28]=[C:11]([C:12]([O:14][CH3:15])=[O:13])[C@H:10]([OH:17])[CH2:9][N:8]1[C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])([C:24]([CH3:26])([CH3:27])[CH3:25])([CH3:22])[CH3:23]

参加物

5

反応物 2

HCID 8857Ethyl Acetate2 回HCID 89851332methyl 4-(tert-butoxycarbonyl((S)-1-(tert-butyldimethylsilyloxy)but-3-en-2-yl)amino)-3-hydroxy-2-methylenebutanoate2 回

生成物 1

HCID 89852366(2S,5S)-1-tert-butyl 4-methyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1,4(2H)-dicarboxylate

試薬・触媒・溶媒 2

HCID 11763533(1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)(dichloro)((2-((propan-2-yl)oxy)phenyl)methylidene)ruthenium触媒HCID 1140Toluene溶媒

実験手順

A stirred solution of methyl 4-(tert-butoxycarbonyl((S)-1-(tert-butyldimethylsilyloxy)but-3-en-2-yl)amino)-3-hydroxy-2-methylenebutanoate (Intermediate 100, 16 g, 37 mmol) in toluene (about 300 mL), at ambient temperature in a heat-dried flask, was thoroughly degassed with argon and placed under a nitrogen atmosphere. To this was added Hoveyda-Grubbs Catalyst 2nd Generation (460 mg, 0.74 mmol). Analysis of the mixture 3.5 hours later by LCMS and TLC (15% ethyl acetate in hexanes) indicated very high conversion of starting material to two major products. The reaction mixture was concentrated in vacuo in the presence of enough silica gel to give a free-flowing powder upon reaching dryness. Normal-phase chromatography (0-100% ethyl acetate in hexanes, 330-g column, 45 minutes) was used to isolate the two compounds; the diastereomer shown above (6.4 g, 43%, dark oil) eluted first.

後処理

  1. customAnalysis of the mixture 3.5 hours
  2. concentrationThe reaction mixture was concentrated in vacuo in the presence of enough silica gel
  3. customto give a free-flowing powder
  4. customto isolate the two compounds
  5. washeluted first

出典と根拠

ORDレコード
ord-9b364beaf4cc40a4948a6847af077977
出典データセット
uspto-grants-2016_04
特許番号
US09309245B2

関連ノート

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