p-Toluenesulfonic acid monohydrate → [(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[3-[(4-benzyloxyphenyl)methyl]-4-chloro-phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol

HRID 1055603Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1055603
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@:12]([C:33]2[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]3[CH:46]=[CH:45][C:44]([O:47][CH2:48][C:49]4[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=4)=[CH:43][CH:42]=3)[CH:34]=2)([O:31][CH3:32])[O:11][C:10]1(CO)[CH2:55][OH:56])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>ClCCl>[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@:12]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:42]=[CH:43][C:44]([O:47][CH2:48][C:49]5[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=5)=[CH:45][CH:46]=4)[CH:34]=3)[O:11][C@@:10]1([CH2:55][OH:56])[CH2:32][O:31]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

4

Edukt 2

HCID 521998p-Toluenesulfonic acid monohydrateHCID 131736399HCID 131736399, Verbindung

Produkt 1

HCID 131736400[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[3-[(4-benzyloxyphenyl)methyl]-4-chloro-phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanolAusbeute 58,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

To a solution of [(3S,4S,5R,6S)-3,4,5-tribenzyloxy-6-[3-[(4-benzyloxyphenyl)methyl]-4-chloro-phenyl]-2-(hydroxymethyl)-6-methoxy-tetrahydropyran-2-yl]methanol 25k (1.04 g, 13 mmol) in dichloromethane (100 mL) was added p-toluenesulfonic acid monohydrate (123 mg, 0.65 mmol) at 0° C. The mixture was warmed up to room temperature and stirred for 16 hours. The reaction mixture was quenched with saturated aqueous sodium bicarbonate (10 mL) and partitioned. The organic layer was washed with water (30 mL×2) and saturated aqueous sodium chloride (30 mL×2) in turn, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo and the residue was purified by silica gel chromatography eluted with PE/EtOAc(v/v)=10/1 to give the title compound 25l as pale yellow oil (0.59 g, 58.7%). The compound was characterized by the following spectroscopic data: 1H NMR (600 MHz, CDCl3) δ(ppm): 7.44 (m, 3H), 7.35 (m, 15H), 7.19 (m, 3H), 7.09 (m, 2H), 6.89 (m, 2H), 6.85 (m, 2H), 5.02 (s, 2H), 4.90 (d, 2H), 4.86 (d, 1H), 4.77 (d, 1H), 4.30 (d, 1H), 4.27 (d, 1H), 4.07 (d, 1H), 4.03 (m, 2H), 3.97 (d, 1H), 3.86 (d, 1H), 3.82 (d, 1H), 3.74 (d, 1H), 3.70 (d, 1H), 3.68 (d, 1H).

Aufarbeitung

  1. customThe reaction mixture was quenched with saturated aqueous sodium bicarbonate (10 mL)
  2. custompartitioned
  3. washThe organic layer was washed with water (30 mL×2) and saturated aqueous sodium chloride (30 mL×2) in turn
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated in vacuo
  7. customthe residue was purified by silica gel chromatography
  8. washeluted with PE/EtOAc(v/v)=10/1

Quellen und Nachweise

ORD-Eintrag
ord-abdc1950c7a44349bcbf9967b93902f8
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09394329B2

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