Iodine → (E)-(1R,6S,7R,10S,21S)-21-benzyl-6-hydroxy-7-isopropyl-2,3-dioxa-12,13-dithia-8,18,23-triaza-bicyclo[8.7.6]tricos-16-ene-4,9,19,22-tetraone

HRID 888674Notes

Reaction equation

HRID 888674 reaction equation
II.[CH2:3]([C@@H:10]1[C:25](=[O:26])[NH:24][C@H:23]([CH2:27][S:28]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[C:22](=[O:48])[NH:21][C@H:20]([CH:49]([CH3:51])[CH3:50])[C@@H:19]([OH:52])[CH2:18][C:17](=[O:53])[O:16][O:15][C@H:14](/[CH:54]=[CH:55]/[CH2:56][CH2:57][S:58]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[NH:13][C:12](=[O:78])[CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl.CO>[CH2:3]([C@@H:10]1[C:25](=[O:26])[NH:24][C@@H:23]2[CH2:27][S:28][S:58][CH2:57][CH2:56][CH:55]=[CH:54][C@@H:14]([O:15][O:16][C:17](=[O:53])[CH2:18][C@H:19]([OH:52])[C@@H:20]([CH:49]([CH3:51])[CH3:50])[NH:21][C:22]2=[O:48])[NH:13][C:12](=[O:78])[CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 807IodineHCID 24477Sodium ThiosulfateHCID 86639714HCID 86639714, compound

Product 1

HCID 86639716(E)-(1R,6S,7R,10S,21S)-21-benzyl-6-hydroxy-7-isopropyl-2,3-dioxa-12,13-dithia-8,18,23-triaza-bicyclo[8.7.6]tricos-16-ene-4,9,19,22-tetraoneYield 68%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent2×

Procedure

To a solution of iodine (198.4 mg, 0.78 mmol) in CH2Cl2/MeOH (9:1, 272 mL) was added dropwise a solution of 6A (79.4 mg, 0.08 mmol) in CH2Cl2/MeOH (9:1) (134 mL) over 30 min, the reaction mixture was then allowed to stir for a further 30 min after which time sodium thiosulfate (88 mL, 0.05 M) was added. The layers were separated and the product was extracted with CH2Cl2 (3×45 ml) dried (MgSO4) and the solvent was removed in vacuo. Purification was then carried out by column chromatography on silica gel (eluent 3:97 MeOH/CH2Cl2) which gave 7A (30 mg, mmol, 68%) as a white solid: Rf 0.19 CH2Cl2/MeOH (97:3); [α]26D=−83.7 (c 0.38, MeOH).

Workup

  1. additionwas added
  2. customThe layers were separated
  3. extractionthe product was extracted with CH2Cl2 (3×45 ml)
  4. dry with materialdried (MgSO4)
  5. customthe solvent was removed in vacuo
  6. customPurification

Sources & evidence

ORD record
ord-449ed05f42bb4d09b6f557ffaf984990
Source dataset
uspto-grants-2012_08
Patent number
US08247372B2

Reaction notes

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