HCID 23657110, compound → HCID 12001305, compound

HRID 1012861Notes

Reaction equation

HRID 1012861 reaction equation
[CH:1]([C@H:4]1[NH:19][C:18](=[O:20])[C@@H:17]([CH2:21][S:22]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[NH:16][C:15](=[O:42])[C@@H:14]([CH:43]([CH3:45])[CH3:44])[NH:13][C:12](=[O:46])[CH2:11][C@@H:10](/[CH:47]=[CH:48]/[CH2:49][CH2:50][S:51]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[O:9][C:8](=[O:71])[CH2:7][NH:6][C:5]1=[O:72])([CH3:3])[CH3:2]>C(Cl)Cl.CO>[CH:1]([C@H:4]1[NH:19][C:18](=[O:20])[C@@H:17]2[NH:16][C:15](=[O:42])[C@@H:14]([CH:43]([CH3:45])[CH3:44])[NH:13][C:12](=[O:46])[CH2:11][C@@H:10]([CH:47]=[CH:48][CH2:49][CH2:50][S:51][S:22][CH2:21]2)[O:9][C:8](=[O:71])[CH2:7][NH:6][C:5]1=[O:72])([CH3:3])[CH3:2]

Participants

3

Reactant 1

HCID 23657110HCID 23657110, compound

Product 1

HCID 12001305HCID 12001305, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent

Procedure

To a vigorously stirred solution of 12 (305 mg, 1.2 mmol) in CH2Cl2/MeOH (9:1, 280 mL) was added dropwise a solution of bis-trityl 8C (120 mg, 0.12 mmol) over 30 minutes. After a further 30 min the reaction was quenched by the addition of sodium thiosulfate (0.05M, 100 mL) followed by brine (10 mL). The organic phase was separated and the aqueous phase extracted with CH2Cl2 (3×15 mL). The combined organic phase was dried (MgSO4), filtered, and concentrated in vacuo to give a white solid. Purification by column chromatography on silica gel (1-4% MeOH/CH2Cl2) gave bicyclic depsipeptide 9C (60 mg, 0.12 mmol, 97%) as a white solid: [α]25D −105.7 (1:1 MeOH/CHCl3, c 0.15); 1H-NMR (400 MHz, CD3OD) δ 5.76-5.63 (m, 3H), 4.52 (dd, J=11.3, 4.7 Hz, 1H), 3.96 (d, J=5.1 Hz, 1H), 3.74 (d, J=17.5 Hz, 1H), 3.38 (d, J=10.9 Hz, 1H), 3.19-3.11 (m, 2H), 3.09-2.96 (m, 3H), 2.90 (dd, J=13.6, 2.5 Hz, 1H), 2.71-2.62 (m, 2H), 2.58-2.44 (m, 1H), 2.31-2.18 (m, 1H), 1.11 (d, J=7.0 Hz, 3H), 1.09 (d, J=7.0 Hz, 3H), 1.01 (d, J=6.6 Hz, 3H), 0.91 (d, J=6.6 Hz, 3H); 13C-NMR (100 MHz, CD3OD) δ 171.8 (C), 171.7 (C), 170.7 (C), 170.4 (C), 168.3 (C), 130.0 (CH), 129.6 (CH), 69.8 (CH), 64.6 (CH), 61.9 (CH), 54.8 (CH), 42.2 (CH2), 39.3 (CH2), 37.5 (CH2), 37.1 (CH2), 32.1 (CH2), 29.2 (CH), 27.3 (CH), 20.6 (CH3), 20.0 (CH3), 19.4 (CH3), 19.0 (CH3); LRMS (ES+) m/z 537 (100%, [M+Na]+), 515 (90%, [M+H]+).

Workup

  1. customAfter a further 30 min the reaction was quenched by the addition of sodium thiosulfate (0.05M, 100 mL)
  2. customThe organic phase was separated
  3. extractionthe aqueous phase extracted with CH2Cl2 (3×15 mL)
  4. dry with materialThe combined organic phase was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto give a white solid
  8. customPurification by column chromatography on silica gel (1-4% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-2c08bb7c64e6423692d88cff86f1f068
Source dataset
uspto-grants-2011_07
Patent number
US07977304B2

Reaction notes

Loading…