Dimethylformamide → HCID 59557717, compound

HRID 1175307Notes

Reaction equation

HRID 1175307 reaction equation
[CH2:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([Cl:12])[C:9]([CH2:13][C:14]2[CH:19]=[CH:18][C:17]([CH2:20][CH3:21])=[CH:16][CH:15]=2)=[CH:8][C:7]=1[C@H:22]1[C@H:27]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@@H:26]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:25]([O:44][CH2:45][C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C@@H:24]([CH2:52][O:53][CH2:54][C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[O:23]1)[CH:2]=[CH2:3].CN(C=[O:65])C>[Pd](Cl)Cl.[Cu](Cl)Cl>[Cl:12][C:10]1[C:9]([CH2:13][C:14]2[CH:15]=[CH:16][C:17]([CH2:20][CH3:21])=[CH:18][CH:19]=2)=[CH:8][C:7]([C@H:22]2[C@H:27]([O:28][CH2:29][C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[C@@H:26]([O:36][CH2:37][C:38]3[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=3)[C@H:25]([O:44][CH2:45][C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[C@@H:24]([CH2:52][O:53][CH2:54][C:55]3[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=3)[O:23]2)=[C:6]([CH:11]=1)[CH2:5][O:4][CH2:1][C:2](=[O:65])[CH3:3]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 59557724HCID 59557724, compound

Product 1

HCID 59557717HCID 59557717, compoundYield 58.2%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 24290Palladium ChlorideCatalyst

Procedure

A mixture of palladium chloride (159 mg, 0.053 mmol) and copper chloride (267 mg, 0.27 mmol) in DMF (3 mL) was stirred for 2.5 h at room temperature. (2S,3S,4R,5R,6R)-2-(2-(allyloxymethyl)-4-chloro-5-(4-ethylbenzyl)phenyl)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran (intermediate O-1) (300 mg, 0.36 mmol) was added to the mixture and stirred overnight under oxygen. The reaction mixture was filtered, the filtrate was poured into water and extracted with ethyl acetate (20 mL×3). The combined extracts were dried over Na2SO4, filtered, and evaporated to dryness. The residue was purified by preparative TLC, which afforded 1-(5-chloro-4-(4-ethylbenzyl)-2-((2S,3S,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran-2-yl)benzyloxy)propan-2-one (intermediate T-1) (178 mg, 0.33 mmol, yield 58.2%). 1H-NMR (DMSO-d6, 300 MHz) δ 1.062 (t, J=8.1 Hz, 3H), 1.988 (s, 3H), 2.452 (dd, J=8.1 Hz, 2H), 3.603 (m, 6H), 3.793 (m, 2H), 3.997 (s, 2H), 4.125 (s, 2H), 4.491 (11, 7H), 4.744 (m, 4H), 6.789 (m, 2H), 7.015 (m, 4H), 7.169 (m, 5H), 7.288 (m, 13H), 7.457 (s, 2H).

Workup

  1. stirringstirred overnight under oxygen
  2. filtrationThe reaction mixture was filtered
  3. additionthe filtrate was poured into water
  4. extractionextracted with ethyl acetate (20 mL×3)
  5. dry with materialThe combined extracts were dried over Na2SO4
  6. filtrationfiltered
  7. customevaporated to dryness
  8. customThe residue was purified by preparative TLC, which

Sources & evidence

ORD record
ord-97dc8a4204054af4871ea7d3f034d8e8
Source dataset
uspto-grants-2010_11
Patent number
US07838498B2

Reaction notes

Loading…