Dimethylformamide → Boc-Leu-DTrp-betaAla-OEt

HRID 2295170Notes

Reaction equation

HRID 2295170 reaction equation
[NH:1]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[C@H:2]([C:7]([NH:9][C@@H:10]([C:21]([NH:23]N)=[O:22])[CH2:11][C:12]1[C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[NH:14][CH:13]=1)=[O:8])[CH2:3][CH:4]([CH3:6])[CH3:5].Cl.O1CCO[CH2:35][CH2:34]1.N([O:41][CH2:42][CH2:43][CH:44](C)C)=O.CN(C=[O:51])C>>[NH:1]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[C@H:2]([C:7]([NH:9][C@@H:10]([C:21]([NH:23][CH2:44][CH2:43][C:42]([O:41][CH2:34][CH3:35])=[O:51])=[O:22])[CH2:11][C:12]1[C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[NH:14][CH:13]=1)=[O:8])[CH2:3][CH:4]([CH3:6])[CH3:5]

Participants

5

Reactant 4

HCID 6228Dimethylformamide2×HCID 8053Isoamyl NitriteHCID 11070055Boc-Leu-DTrp-NHNH2HCID 204431481,4-Dioxane hydrochloride

Product 1

HCID 131719104Boc-Leu-DTrp-betaAla-OEt

Conditions

Temperature
-20 °C

Procedure

To a solution of Boc-Leu-DTrp-NHNH2 (39 mg) obtained in Example 1-(2) in DMF (0.5 ml) was added 3.1M HCl/1,4-dioxane (81 μl ) at -60° C. The temperature of the solution was raised to -20° C. and isoamyl nitrite (15 μl ) was added. The reaction mixture was stirred at -20° C. to -15° C. for 1.5 h and cooled at -60 ° C. A solution of βAla-OEt·HCI (17 mg) in DMF (0.5 ml) and TEA (50 μl ) were added. The reaction mixture was stirred at 5° C. overnight and concentrated under reduced pressure. The residue was partitioned between water and dichloromethane. The organic layer was washed with water, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by preparative TLC (Merck, Kieselgel 60 F254) with chloroform/methanol=30/1 for development to give the product (41 mg).

Workup

  1. temperaturecooled at -60 ° C
  2. stirringThe reaction mixture was stirred at 5° C. overnight
  3. concentrationconcentrated under reduced pressure
  4. customThe residue was partitioned between water and dichloromethane
  5. washThe organic layer was washed with water
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by preparative TLC (Merck, Kieselgel 60 F254) with chloroform/methanol=30/1 for development

Sources & evidence

ORD record
ord-08e17fec5aea426584196685d2256c34
Source dataset
uspto-grants-1997_11
Patent number
US05691315

Reaction notes

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