HCID 86630475, compound → HCID 12001304, compound

HRID 1012859Notes

Reaction equation

HRID 1012859 reaction equation
[CH2:1]([C@H:8]1[NH:23][C:22](=[O:24])[CH2:21][C@@H:20](/[CH:25]=[CH:26]/[CH2:27][CH2:28][S:29]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[O:19][C:18](=[O:49])[CH2:17][NH:16][C:15](=[O:50])[C@@H:14]([CH:51]([CH3:53])[CH3:52])[NH:13][C:12](=[O:54])[C@@H:11]([CH2:55][S:56]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[NH:10][C:9]1=[O:76])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>C(Cl)Cl.CO>[CH2:1]([C@@H:8]1[C:9](=[O:76])[NH:10][C@@H:11]2[CH2:55][S:56][S:29][CH2:28][CH2:27][CH:26]=[CH:25][C@@H:20]([O:19][C:18](=[O:49])[CH2:17][NH:16][C:15](=[O:50])[C@@H:14]([CH:51]([CH3:53])[CH3:52])[NH:13][C:12]2=[O:54])[CH2:21][C:22](=[O:24])[NH:23]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

3

Reactant 1

HCID 86630475HCID 86630475, compound

Product 1

HCID 12001304HCID 12001304, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent

Procedure

To a vigorously stirred solution of 12 (254 mg, 1.0 mmol) in CH2Cl2/MeOH (9:1, 230 mL) was added dropwise a solution of bis-trityl 8B (105 mg, 0.10 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 (1-3.5% MeOH/CH2Cl2) gave bicyclic depsipeptide 9B (43 mg, 0.08 mmol, 75%) as a white solid: [α]25D −98 (c 0.05, 1:1 MeOH/CHCl3); IR νmax 3280, 1732, 1627, 1538, 1445 cm−1; 1H-NMR (400 MHz, 19:1 CD3OD/CDCl3) δ 7.35-7.18 (m, 5H), 5.86-5.76 (m, 1H), 5.74-5.66 (m, 2H), 4.62 (dd, J=11.3, 4.0 Hz, 1H), 4.45 (dd, J=9.3, 5.3 Hz, 1H), 4.28 (d, J=17.6 Hz, 1H), 3.77 (d, J=17.6 Hz, 1H), 3.39 (d, J=10.5 Hz, 1H), 3.27-3.17 (m, 2H), 3.11-2.99 (m, 3H), 2.97-2.83 (m, 2H), 2.81 (dd, J=13.6, 2.0 Hz, 1H), 2.70-2.53 (m, 3H), 0.96 (d, J=6.5 Hz, 3H), 0.92 (d, J=6.5 Hz, 3H); 13C-NMR (100 MHz, 19:1 CD3OD/CDCl3) δ 173.8 (C), 173.2 (C), 172.9 (C), 171.3 (C), 169.4 (C), 137.7 (CH), 131.3 (CH), 131.3 (CH), 129.7 (CH), 129.6 (CH), 128.0 (CH), 71.9 (CH), 65.9 (CH), 58.3 (CH), 58.1 (CH), 42.6 (CH2), 39.3 (2×CH2), 36.9 (CH2), 36.8 (CH2), 31.8 (CH2), 28.1 (CH), 20.6 (CH3), 20.5 (CH3); LRMS (ES+) m/z 580 (50%, [2M+Na]+), 563 (100%, [M+NH4]+), 563 (10% [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 (1-3.5% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-d543e6e5b1c54082a7b60d6577965dae
Source dataset
uspto-grants-2011_07
Patent number
US07977304B2

Reaction notes

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