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Ammonium Chloride → (2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-carbamoyl-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627121
ノート
印刷プレビュー

反応式

HRID 627121 の反応式
[CH2:1]([O:4][N:5]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C@H:6]1[CH2:11][N:10]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C@H:9]([CH2:19][OH:20])[CH:8]=[C:7]1[CH2:21][O:22][CH3:23])[CH:2]=[CH2:3].I([O-])(=O)(=O)=O.[Na+].OS([O-])=O.[Na+].C(O[N:46](C(OC(C)(C)C)=O)[C@H]1CN(C(OC(C)(C)C)=O)[C@H](C(O)=O)C=C1COC)C=C.[Cl-].[NH4+].CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C>CC#N.C(OCC)(=O)C.CN(C=O)C>[CH2:1]([O:4][N:5]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C@H:6]1[CH2:11][N:10]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C@H:9]([C:19](=[O:20])[NH2:46])[CH:8]=[C:7]1[CH2:21][O:22][CH3:23])[CH:2]=[CH2:3]
参加物実験手順後処理出典と根拠反応ノート

参加物

11

反応物 7

HCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 23665763Sodium BisulfiteHCID 23667635Sodium periodate
HCID 89851341
(2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-(hydroxymethyl)-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate
2 回
HCID 89852905(2S,5R)-5-(allyloxy(tert-butoxycarbonyl)amino)-1-(tert-butoxycarbonyl)-4-(methoxymethyl)-1,2,5,6-tetrahydropyridine-2-carboxylic acid

生成物 1

HCID 89852023(2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-carbamoyl-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate収率 43.3%

試薬・触媒・溶媒 3

HCID 6228Dimethylformamide溶媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒2 回

実験手順

To a stirred solution of (2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-(hydroxymethyl)-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 72, 8.82 g, 20.58 mmol) in 100 mL MeCN at 0° C., was added sodium periodate (19.37 g, 90.56 mmol). Then 12 mL of the stock oxidation solution was added. The suspension was then stirred at rt for 2d. An additional 16 mL the above stock solution was added and stirred for 2 more days. The mixture was diluted with 150 mL ethyl acetate, 50 mL 1M pH 7 buffer, and 50 mL 2M NaHSO3. The aqueous was extracted with 20 mL ethyl acetate. The ethyl acetate layer was then washed with brine. The aqueous layer was checked by LCMS and found containing desired carboxylic acid. The aqueous layer was then extracted with 50 mL ethyl acetate and washed with brine. The combined organic layers was dried over MgSO4, filtered and concentrated to afford a yellow dry film, (crude 7.11 g, 78%) which was used directly without further purification. To a stirred solution of (2S,5R)-5-(allyloxy(tert-butoxycarbonyl)amino)-1-(tert-butoxycarbonyl)-4-(methoxymethyl)-1,2,5,6-tetrahydropyridine-2-carboxylic acid (crude, 7.11 g, 16.07 mmol), ammonium chloride (1.719 g, 32.14 mmol), HATU (12.22 g, 32.14 mmol) in DMF (50.0 mL) at rt, was added DIPEA (8.31 g, 64.27 mmol). After stirring at rt for 1 hr, 100 mL EtOAc was added. The organic layer was washed with water, brine. The residue was purified by silica gel column (0-100% Hex/EA) to afford the desired product (3.07 g, 43.3%) as an off-white solid.

後処理

  1. additionThen 12 mL of the stock oxidation solution was added
  2. extractionThe aqueous was extracted with 20 mL ethyl acetate
  3. washThe ethyl acetate layer was then washed with brine
  4. additionfound containing desired carboxylic acid
  5. extractionThe aqueous layer was then extracted with 50 mL ethyl acetate
  6. washwashed with brine
  7. dry with materialThe combined organic layers was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford a yellow dry film
  11. custom(crude 7.11 g, 78%) which was used directly without further purification
  12. stirringAfter stirring at rt for 1 hr
  13. washThe organic layer was washed with water, brine
  14. customThe residue was purified by silica gel column (0-100% Hex/EA)

出典と根拠

ORDレコード
ord-3752e13d3e464af3b92b724b5d90a003
出典データセット
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09309245B2

反応ノート

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このページの内容参加物実験手順後処理出典と根拠反応ノート