Tributylphosphine → methyl 4-bromo-3-{(1S)-2-[(tert-butoxycarbonyl)amino]-1-methylethoxy}thiophene-2-carboxylate

HRID 1404981Notes

Reaction equation

HRID 1404981 reaction equation
[Br:1][C:2]1[C:3]([OH:11])=[C:4]([C:7]([O:9][CH3:10])=[O:8])[S:5][CH:6]=1.O[C@H:13]([CH3:23])[CH2:14][NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19].C(P(CCCC)CCCC)CCC.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[Br:1][C:2]1[C:3]([O:11][C@@H:13]([CH3:23])[CH2:14][NH:15][C:16]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:22])=[C:4]([C:7]([O:9][CH3:10])=[O:8])[S:5][CH:6]=1

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 2777611Methyl 4-bromo-3-hydroxythiophene-2-carboxylateHCID 12094522N-Boc-(R)-1-amino-2-propanol

Product 1

HCID 67958910methyl 4-bromo-3-{(1S)-2-[(tert-butoxycarbonyl)amino]-1-methylethoxy}thiophene-2-carboxylateYield 65%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 4-bromo-3-hydroxythiophene-2-carboxylate (237 mg), tert-butyl [(2R)-2-hydroxypropyl]carbamate (175 mg), tri-n-butylphosphine (0.75 mL) and THF (10 mL) was added dropwise diethyl azodicarboxylate (40% toluene solution, 1.4 mL) at room temperature, and the mixture was stirred for 2 hr. The reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (solvent gradient; 0→15% ethyl acetate/hexane) to give the title compound (239 mg, 65%) as a colorless oil.

Workup

  1. concentrationThe reaction solution was concentrated under reduced pressure
  2. customthe residue was purified by silica gel column chromatography (solvent gradient; 0→15% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-e99a8ec113e8466f9f3ec32932fd3c42
Source dataset
uspto-grants-2014_12
Patent number
US08916549B2

Reaction notes

Loading…