Dimedone → HCID 22177643, compound

HRID 1797386Notes

Reaction equation

HRID 1797386 reaction equation
C([O:4][C:5](=[O:38])[CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([CH:18]2[O:22][CH:21]3[CH:23]([CH2:36][OH:37])[O:24][CH:25]([N:26]4[CH:34]=[N:33][C:32]5[C:27]4=[N:28][CH:29]=[N:30][C:31]=5[Cl:35])[CH:20]3[O:19]2)=[CH:14][CH:13]=1)C=C.CC1(C)CC(=O)CC(=O)C1>C(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:35][C:31]1[N:30]=[CH:29][N:28]=[C:27]2[C:32]=1[N:33]=[CH:34][N:26]2[CH:25]1[CH:20]2[CH:21]([O:22][CH:18]([C:15]3[CH:14]=[CH:13][C:12]([O:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][C:5]([OH:38])=[O:4])=[CH:17][CH:16]=3)[O:19]2)[CH:23]([CH2:36][OH:37])[O:24]1

Participants

5

Reactant 2

HCID 31358DimedoneHCID 87901041HCID 87901041, compound

Product 1

HCID 22177643HCID 22177643, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 5 (59.31 g, 108.8 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 12.6 g, 10.9 mmol), and dimedone (45.7 g, 326.4 mmol) in dry DCM (600 mL) was stirred in a nitrogen atmosphere for 3.5 h at room temperature. 500 ml of the solvent was removed in vacuo and the remaining volume was loaded on a silica plug. After the dimedone byproducts were removed by washing the plug with MeOH/DCM 1:100, the product was eluted with MeOH/DCM 1:10. The fraction containing the product was concentrated in vacuo to afford 6 as a white powder (46.6 g, 92.3 mmol, 85%) as a mixture of two diastereomers: M.p.: 127-129° C.; 1H-NMR (400 MHz, CDCl3) δ=11.50 (s, 1H, 1H′), 8.79 (s, 1H), 8.78 (s, 1H′), 8.42 (s, 1H), 8.34 (s, 1H′), 7.47 (d, J=8.6, 2H), 7.37 (d, J=8.6, 2H′), 6.95 (d, J=8.5, 2H), 6.90 (d, J=8.5, 2H′), 6.24 (s, 1H), 6.19 (m, 1H, 1H′), 6.02 (s, 1H′), 5.37-5.19 (m, 2H, 2H′), 4.73 (s, 1H, 1H′), 4.57 (m, 1H, 1H′), 4.04-3.86 (m, 4H, 4H′), 2.40 (m, 2H, 2H′), 1.82 (m, 2H, 2H′), 1.72 (m, 2H, 2H′), 1.55 (m, 2H, 2H′); 13C-NMR (400 MHz, CDCl3) δ=178.8, 178.8, 160.6, 160.5, 152.3, 152.2, 150.6, 150.6, 133.4, 133.3, 132.2, 132.2, 128.3 (2C),128.1, 128.0 (2C), 127.6, 114.9, 114.9, 114.8 (2C), 114.7 (2C), 108.1, 105.1, 94.0, 92.0, 86.4, 86.3, 84.2, 83.5, 83.5, 80.5, 68.0, 67.9, 63.3, 63.0, 34.0, 34.0, 29.0, 29.0, 25.8, 25.8, 24.6, 24.6; IR (film) ν=3292, 3109, 3074, 2938, 1708, 1595, 1392, 1245, 1225, 1194, 1108, 1069, 828; HRMS (MALDI-FTMS) m/z 527.1285 (527.1304 calculated for C23H25N4O7ClNa (M+Na)+).

Workup

  1. custom500 ml of the solvent was removed in vacuo
  2. customAfter the dimedone byproducts were removed
  3. washby washing the plug with MeOH/DCM 1:100
  4. washthe product was eluted with MeOH/DCM 1:10
  5. additionThe fraction containing the product
  6. concentrationwas concentrated in vacuo

Sources & evidence

ORD record
ord-9bb683bc3e07444a9eb9b8959c8f8cc6
Source dataset
uspto-grants-2006_04
Patent number
US07034147B2

Reaction notes

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