HCID 86674679, compound → HCID 86674678, compound

HRID 1523008Notes

Reaction equation

HRID 1523008 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15]/[C:16](/[Sn](CCCC)(CCCC)CCCC)=[CH:17]\[C:18]([O:20][CH3:21])=[O:19]>Cl[Cu].CN(C=O)C>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15]/[C:16](/[C:16](/[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][O:7][CH:2]1[CH2:3][CH2:4][CH2:5][CH2:6][O:1]1)=[CH:17]/[C:18]([O:20][CH3:21])=[O:19])=[CH:17]\[C:18]([O:20][CH3:21])=[O:19]

Participants

4

Reactant 1

HCID 86674679HCID 86674679, compound

Product 1

HCID 86674678HCID 86674678, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 6228DimethylformamideSolvent

Procedure

To a flamed-dried round-bottomed flask was added (E)-methyl 11-((tetrahydro-2H -pyran-2-yl)oxy)-3-(tributylstannyl)undec-2-enoate (1 equiv, 25.5 mmol, 15.0 g), DMF (30 mL), and CuCl (3 equiv, 76.5 mmol, 7.57 g). The reaction was stirred for 3 h at rt, quenched with aq. NH4Cl/NH4OH (pH ˜8) (35 mL), and stirred for 2 h open to the air. The solution was diluted with H2O (50 mL) and Et2O (50 mL). The layers are separated and the aqueous layer was extracted with Et2O (2×50 mL). The combined organic layers were washed with brine (75 mL), dried with MgSO4, concentrated in vacuo, and purified by flash chromatography (step gradient, 10% EtOAc/Hex to 15% EtOAc/Hex) to afford (2E,4E)-dimethyl 3,4-bis(8-((tetrahydro-2H-pyran-2-yl)oxy)octyl)hexa-2,4-dienedioate (6.27 g, 10.5 mmol, 83%). TLC Rf=0.19 (10% EtOAc/Hex); 1HNMR (500 MHz): δ 5.84 (bs, 2H), 4.55-4.61 (2H), 3.83-3.92 (2H), 3.69-3.77 (s plus ovlp. m, 8H), 3.47-3.55 (m, 2H), 3.38 (dt, 2H, J1=9.6 Hz, J2=6.7 Hz), 2.72-2.84 (4H), 1.78-1.89 (2H), 1.69-1.76 (2H), 1.50-1.63 (12H), 1.28-1.41 (20H); 13CNMR (125 MHz): δ 166.5, 161.8, 117.6, 98.8, 67.7, 62.3, 51.2, 30.8, 29.7, 29.6, 29.4, 29.3, 29.1, 28.7, 26.2, 25.5, 19.7; FTIR: 2927, 2855, 1718, 1628, 1433, 1351, 1193, 1163, 1136, 1078, 1023, 986, 905, 868, 814 cm−1; HRMS-ESI: calc. for C34H58NaO8 (M+Na)+: 617.4029. found: 617.4039.

Workup

  1. customquenched with aq. NH4Cl/NH4OH (pH ˜8) (35 mL)
  2. stirringstirred for 2 h open to the air
  3. additionThe solution was diluted with H2O (50 mL) and Et2O (50 mL)
  4. customThe layers are separated
  5. extractionthe aqueous layer was extracted with Et2O (2×50 mL)
  6. washThe combined organic layers were washed with brine (75 mL)
  7. dry with materialdried with MgSO4
  8. concentrationconcentrated in vacuo
  9. custompurified by flash chromatography (step gradient, 10% EtOAc/Hex to 15% EtOAc/Hex)

Sources & evidence

ORD record
ord-9c05fb6e851f45df9ba763fc816414ff
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

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