Toluene → HCID 86681903, compound

HRID 1020895Notes

Reaction equation

HRID 1020895 reaction equation
[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@@H:12]([CH2:31][O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[O:11][C@H:10]1[O:40][C@H:41]1[C@H:50]([OH:51])[C@@H:49]([CH2:52][OH:53])[O:48][C@H:43]([O:44][CH2:45][CH:46]=[CH2:47])[C@@H:42]1[O:54][CH2:55][C:56]1[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:62][O:63][C:64]1[CH:69]=[CH:68][C:67](O)=[CH:66][CH:65]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.C1(C)C=CC=CC=1>C(Cl)Cl>[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:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[C@@H:12]([CH2:31][O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[O:11][C@H:10]1[O:40][C@H:41]1[C@H:50]([OH:51])[C@@H:49]([CH2:52][O:53][C:67]2[CH:68]=[CH:69][C:64]([O:63][CH3:62])=[CH:65][CH:66]=2)[O:48][C@H:43]([O:44][CH2:45][CH:46]=[CH2:47])[C@@H:42]1[O:54][CH2:55][C:56]1[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 5

HCID 1140TolueneHCID 90154-MethoxyphenolHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 86681904HCID 86681904, compound

Product 1

HCID 86681903HCID 86681903, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Allyl 3-O-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-2-O-benzyl-α-D-glucopyranoside 14 (10.1 g, 12.1 mmol), 4-methoxyphenol (3.76 g, 30.3 mmol), and triphenylphosphine (4,77 g, 18.2 mmol) were combined in a flask, cooled to 0° C. before adding anhydrous CH2Cl2 (100 mL). This solution was stirred for 40 minutes and then a solution of diethylazodicarboxylate (DEAD) in toluene (40% by weight, 8.84 mL, 19.4 mmol) was added. The reaction mixture was stirred at 0° C. for 45 minutes, and then allowed to warm to room temperature overnight. The reaction mixture was diluted with CH2Cl2, washed with 1N NaOH (200 mL, 100 mL), 1 N HCl (200 mL), saturated NaHCO3 (200 mL), and brine, dried over Na2SO4, filtered and concentrated. The residue was purified on a silica gel column eluted using an ethyl acetate:heptane step gradient (1:10→1:5→1:3) to give allyl 3-O-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-2-O-benzyl-6-O-(4-methoxyphenyl)-α-D-glucopyranoside 14 (7.81 g, 69%).

Workup

  1. stirringThe reaction mixture was stirred at 0° C. for 45 minutes
  2. temperatureto warm to room temperature overnight
  3. washwashed with 1N NaOH (200 mL, 100 mL), 1 N HCl (200 mL), saturated NaHCO3 (200 mL), and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified on a silica gel column
  8. washeluted

Sources & evidence

ORD record
ord-21597fe32dd64fc4bb11059a36b327c3
Source dataset
uspto-grants-2014_05
Patent number
US08716469B2

Reaction notes

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