Phosphine → 3-(2-Azido-1-methyl-ethylamino)-5-phenyl-thiophene-2-carboxylic acid methyl ester

HRID 73218

Reaction equation

HRID 73218 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:8][C:9]=1[NH:10][CH:11]([CH3:14])[CH2:12]O)=[O:4].C(OC([N+](C(OCC)=O)=[N-])=O)C.C1(P([N:47]=[N+:48]=[N-:49])(C2C=CC=CC=2)=O)C=CC=CC=1.P>>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:8][C:9]=1[NH:10][CH:11]([CH3:14])[CH2:12][N:47]=[N+:48]=[N-:49])=[O:4]

Participants

5

Reactant 4

HCID 24404PhosphineHCID 199401P,P-Diphenylphosphinic azideHCID 14357405DiethyldiazodicarboxylateHCID 597523863-(2-Hydroxy-1-methyl-ethylamino)-5-phenyl-thiophene-2-carboxylic acid methyl ester

Product 1

HCID 597523333-(2-Azido-1-methyl-ethylamino)-5-phenyl-thiophene-2-carboxylic acid methyl ester

Procedure

A mixture of 3-(2-Hydroxy-1-methyl-ethylamino)-5-phenyl-thiophene-2-carboxylic acid methyl ester (213 mg, 0.257 mmol), diethyldiazodicarboxylate (250 μL, 1.59 mmol, 2 eq), diphenylphosphoryl azide (343 μL, 1.59 mmol, 2 eq) and trphenyl phosphine (417 mg, 1.59 mmol, 2 eq) was stirred at 21° until all starting alcohol was consumed. The reaction was evaporated to dryness and the crude residue purified on biotage with 5% EtOAc/hexane followed by 100% toluene as eluent. 3-(2-Azido-1-methyl-ethylamino)-5-phenyl-thiophene-2-carboxylic acid methyl ester was isolated as a solid (181 mg, 78%); 1H NMR (300 MHz, CDCl3) 1.33 (d, J=6.6 Hz, 3H), 3.38-3.46 (m, 2H), 3.78-3.81 (m, 1H), 6.82 (s, 1H), 7.36-7.41 (m, 3H), 7.60-7.62 (m, 2H).

Workup

  1. customwas consumed
  2. customThe reaction was evaporated to dryness
  3. customthe crude residue purified on biotage with 5% EtOAc/hexane

Sources & evidence

ORD record
ord-8747dc51e29b4e1a9a2146977d9a62d9
Source dataset
uspto-grants-2014_09
Patent number
US08829030B2

Linked notes

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