Ethyl propiolate → HCID 68877294, compound

HRID 2112403Notes

Reaction equation

HRID 2112403 reaction equation
[NH2:1][C:2]1[C:3]2[C:10](I)=[CH:9][N:8]([C@@H:12]3[O:18][C@H:17]([CH2:19][OH:20])[C@@H:15]([OH:16])[C@H:13]3[OH:14])[C:4]=2[N:5]=[CH:6][N:7]=1.[C:21]([O:25][CH2:26][CH3:27])(=[O:24])[C:22]#[CH:23]>CN(C=O)C.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:26]([O:25][C:21](=[O:24])[C:22]#[C:23][C:10]1[C:3]2[C:2]([NH2:1])=[N:7][CH:6]=[N:5][C:4]=2[N:8]([C@@H:12]2[O:18][C@H:17]([CH2:19][OH:20])[C@@H:15]([OH:16])[C@H:13]2[OH:14])[CH:9]=1)[CH3:27]

Participants

6

Reactant 2

HCID 12182Ethyl propiolateHCID 972975-Iodotubercidin

Product 1

HCID 68877294HCID 68877294, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
55 °C

Procedure

To a solution of the product from Step 5 (61 mg, 0.156 mmol) in DMF (2 mL) were added CuI (6 mg, 0.032 mmol) and TEA (45 μL, 0.323 mmol). The mixture was degassed with argon under sonication for 2-3 minutes and Pd(PPh3)4 (18 mg, 0.016 mmol) was added and the resulting mixture was heated at 55° C. for 15 min. Ethyl propiolate (4×5 μL, 0.197 mmol) was added to the reaction mixture at 55° C. in 30 minutes intervals. The crude mixture was concentrated and purified on silica gel with CH2Cl2/MeOH (100/1, 50/1, 25/1) as the eluents to afford 36 mg (64%) of the target compound.

Workup

  1. customThe mixture was degassed with argon under sonication for 2-3 minutes
  2. concentrationThe crude mixture was concentrated
  3. custompurified on silica gel with CH2Cl2/MeOH (100/1, 50/1, 25/1) as the eluents

Sources & evidence

ORD record
ord-ceaa8989a5a84b10bcc7939351ea0aa0
Source dataset
uspto-grants-2009_04
Patent number
US07524825B2

Reaction notes

Loading…