Di-tert-butyl azodicarboxylate → Di-tert-butyl 1-(5-formylthiophen-3-yl)hydrazine-1,2-dicarboxylate

HRID 2196498Notes

Reaction equation

HRID 2196498 reaction equation
[CH:1]([C:3]1[S:7][CH:6]=[C:5](B(O)O)[CH:4]=1)=[O:2].[N:11]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])=[N:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14]>C1COCC1.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH:1]([C:3]1[S:7][CH:6]=[C:5]([N:11]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[NH:12][C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH:4]=1)=[O:2]

Participants

5

Reactant 2

HCID 97268Di-tert-butyl azodicarboxylateHCID 110841152-Formylthiophene-4-boronic acid

Product 1

HCID 59843289Di-tert-butyl 1-(5-formylthiophen-3-yl)hydrazine-1,2-dicarboxylateYield 86%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 5-formylthiophen-3-ylboronic acid (2 g, 12.82 mmol) and di-tert-butyl azodicarboxylate (1.476 g, 6.41 mmol) in THF (12 mL) under nitrogen was added copper(II) acetate (0.116 g, 0.641 mmol) in one portion according to the procedure of T. Uemura and N. Chatani (J. Org. Chem. 2005, 70, 8631-8634). The suspension was then stirred for 18.5 hours at room temperature. The resulting brown solution was then concentrated and the residue was dissolved in DCM and methanol and loaded on silica and applied to a 40M Biotage column. Elution with a gradient of 10 to 20% ethyl acetate in hexanes gave compound 11 (1.888 g, 86%) as a yellow crust. LRMS (ESI): calc. 342.12; found 365.2 (MNa)+.

Workup

  1. concentrationThe resulting brown solution was then concentrated
  2. dissolutionthe residue was dissolved in DCM
  3. washElution with a gradient of 10 to 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-10c568ba34ec4f0c8e28401475fcefa8
Source dataset
uspto-grants-2012_12
Patent number
US08338437B2

Reaction notes

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