Iodine → HCID 12001302, compound

HRID 1012862Notes

Reaction equation

HRID 1012862 reaction equation
II.[C:3]([O:7][C:8](=[O:80])[CH2:9][CH2:10][C@H:11]1[NH:26][C:25](=[O:27])[CH2:24][C@@H:23](/[CH:28]=[CH:29]/[CH2:30][CH2:31][S:32]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[O:22][C:21](=[O:52])[CH2:20][NH:19][C:18](=[O:53])[C@@H:17]([CH:54]([CH3:56])[CH3:55])[NH:16][C:15](=[O:57])[C@@H:14]([CH2:58][S:59]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[NH:13][C:12]1=[O:79])([CH3:6])([CH3:5])[CH3:4]>C(Cl)Cl.CO>[C:3]([O:7][C:8](=[O:80])[CH2:9][CH2:10][C@@H:11]1[C:12](=[O:79])[NH:13][C@@H:14]2[CH2:58][S:59][S:32][CH2:31][CH2:30][CH:29]=[CH:28][C@@H:23]([O:22][C:21](=[O:52])[CH2:20][NH:19][C:18](=[O:53])[C@@H:17]([CH:54]([CH3:56])[CH3:55])[NH:16][C:15]2=[O:57])[CH2:24][C:25](=[O:27])[NH:26]1)([CH3:6])([CH3:5])[CH3:4]

Participants

4

Reactant 2

HCID 807IodineHCID 87352383HCID 87352383, compound

Product 1

HCID 12001302HCID 12001302, compoundYield 69.6%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent

Procedure

To a solution of I2 (117 mg, 0.46 mmol) in CH2Cl2/MeOH (9:1, 130 mL) was added dropwise a solution of bis-trityl 8F (50 mg, 0.046 mmol) over 30 minutes. After a further 30 min the reaction was quenched by the addition of sodium thiosulfate (0.05M, 50 mL) followed by brine (20 mL). The organic phase was separated and the aqueous phase extracted with CH2Cl2 (3×25 mL). The combined organic phase was dried (MgSO4) before concentration in vacuo gave a white solid. Purification by column chromatography on silica gel (1-3% MeOH/CH2Cl2) gave bicyclic depsipeptide 9F (19 mg, 0.032 mmol, 69%) as a white solid: [α]25D −76.7 (c 0.60, MeOH); 1H-NMR (400 MHz, CDCl3) δ 8.15 (d, J=4.0 Hz, 1H), 7.35 (d, J=6.5 Hz, 1H), 7.23 (t, J=5.5 Hz, 1H), 7.11 (d, J=9.0 Hz, 1H), 6.05 (ddt, J=15.5, 7.0, 2.0 Hz, 1H), 5.84-5.73 (m, 2H), δ 4.97 (td, J=8.0, 4.5 Hz, 1H), 4.18-4.01 (m, 3H), 3.61 (dd, J=15.1, 8.0 Hz, 1H), 3.24 (dd, J=10.5, 6.5 Hz, 1H), 2.95-2.75 (m, 5H), 2.73-2.62 (m, 3H), 2.51 (dd, J=13.6, 2.0 Hz, 1H), 2.42 (ddd, J=18.0, 9.0, 3.5 Hz, 1H), 2.19-2.04 (m, 2H), 1.83 (s, 9H), 0.98 (d, J=6.5 Hz, 3H), 0.92 (d, J=6.5 Hz, 3H); 13C-NMR (100 MHz, CDCl3) δ 175.7 (C), 171.8 (C), 171.7 (C), 170.9 (C), 169.9 (C), 168.2 (C), 130.2 (CH), 129.6 (CH), 82.6 (C), 69.4 (CH), 65.4 (CH), 57.6 (CH), 53.8 (CH), 42.4 (CH2), 40.0 (2×CH2), 38.6 (CH2), 34.1 (CH2), 33.1 (CH2), 28.2 (CH3), 27.4 (CH), 24.9 (CH2), 20.6 (CH3), 20.2 (CH3); LRMS (ES+) m/z 623 (90%, [M+Na]+), 601 (100%, [M+H]+).

Workup

  1. customAfter a further 30 min the reaction was quenched by the addition of sodium thiosulfate (0.05M, 50 mL)
  2. customThe organic phase was separated
  3. extractionthe aqueous phase extracted with CH2Cl2 (3×25 mL)
  4. dry with materialThe combined organic phase was dried (MgSO4)
  5. concentrationbefore concentration in vacuo
  6. customgave a white solid
  7. customPurification by column chromatography on silica gel (1-3% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-82cfe19ac7e34315ac923aa882117f2b
Source dataset
uspto-grants-2011_07
Patent number
US07977304B2

Reaction notes

Loading…