Vinyl Acetate → (1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[2-(benzyloxy)-5-[4-[(1E)-3-carboxyprop-1-en-1-yl]benzyl]-4-methylphenyl]-D-glucitol

HRID 1009865Notes

Reaction equation

HRID 1009865 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[C:40]1[CH:45]=[C:44]([CH2:46][C:47]2[CH:52]=[CH:51][C:50](Br)=[CH:49][CH:48]=2)[C:43]([CH3:54])=[CH:42][C:41]=1[O:55][CH2:56][C:57]1[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:63]([O:66]C=C)(=[O:65])[CH3:64].[CH3:69][C:70]1C(P(C2C(C)=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(#N)C>[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[C:40]1[CH:45]=[C:44]([CH2:46][C:47]2[CH:52]=[CH:51][C:50](/[CH:69]=[CH:70]/[CH2:64][C:63]([OH:66])=[O:65])=[CH:49][CH:48]=2)[C:43]([CH3:54])=[CH:42][C:41]=1[O:55][CH2:56][C:57]1[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 7904Vinyl AcetateHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 67305342(1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[2-(benzyloxy)-5-(4-bromobenzyl)-4-methylphenyl]-D-glucitol

Product 1

HCID 67303958(1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[2-(benzyloxy)-5-[4-[(1E)-3-carboxyprop-1-en-1-yl]benzyl]-4-methylphenyl]-D-glucitolYield 429.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

To an acetonitrile solution (8.8 mL) of (1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[2-(benzyloxy)-5-(4-bromobenzyl)-4-methylphenyl]-D-glucitol (780 mg, 0.876 mmol) were added vinyl acetate (184 mg, 2.14 mmol), palladium(II) acetate (20 mg, 0.0890 mmol), tri-O-tolylphosphine (54 mg, 0.177 mmol) and triethylamine (0.64 mL, 4.38 mmol), and reacted at 120° C. for 20 minutes with microwave manufactured by Biotage. The reaction solution was evaporated under reduced pressure. Thus obtained residue was purified with silica gel column chromatography (hexane:ethyl acetate=5:1, chloroform:methanol=40:1) to obtain the title compound (681 mg, 87%) as an orange-yellow amorphous compound.

Workup

  1. customreacted at 120° C. for 20 minutes with microwave
  2. customThe reaction solution was evaporated under reduced pressure
  3. customThus obtained residue was purified with silica gel column chromatography (hexane:ethyl acetate=5:1, chloroform:methanol=40:1)

Sources & evidence

ORD record
ord-67fd0d3abeab4732aef08283f4354e82
Source dataset
uspto-grants-2011_07
Patent number
US07973012B2

Reaction notes

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