HCID 76831218, compound → HCID 76831278, compound

HRID 1186164Notes

Reaction equation

[CH2:1]([O:4][C:5](=[O:17])[C:6]([C:9]1[CH:14]=[C:13]([Br:15])[CH:12]=[CH:11][C:10]=1[F:16])=[N+]=[N-])[CH:2]=[CH2:3]>C(Cl)Cl.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.[Rh+2].[Rh+2]>[Br:15][C:13]1[CH:12]=[CH:11][C:10]([F:16])=[C:9]([C:6]23[CH2:3][CH:2]2[CH2:1][O:4][C:5]3=[O:17])[CH:14]=1

Participants

Conditions

Temperature: 23 °C

Procedure

To a solution of commercially available rhodium(II) octanoate dimer (Rh2(C7H16CO2)4) ([CAS No. 73482-96-9], 160 mg, 1 mol %) in DCM (60 ml) at 45° C. was added a solution of (5-bromo-2-fluoro-phenyl)-diazo-acetic acid allyl ester (intermediate B4A) (6.0 g, 20 mmol) in DCM (2×20 ml) via syringe pump within 16 h. Continued refluxing for 1 h, cooled to 23° C., washed with 1 M aqueous hydrochloric acid (HCl) and sat. aqueous sodium hydrogencarbonate solution (NaHCO3-sol.), dried organic layer over sodium sulfate. Removal of the solvent in vacuum left a green solid, which was purified by silica gel column chromatography with n-heptane/ethyl acetate to give the title compound as a light green solid (4.6 g, 85%) [cf. Adv. Synth. Catal. 2001, 343, 299, for an enantioselective version of this reaction].

Workup

temperatureContinued refluxing for 1 h
washwashed with 1 M aqueous hydrochloric acid (HCl) and sat. aqueous sodium hydrogencarbonate solution (NaHCO3-sol.), dried organic layer over sodium sulfate
customRemoval of the solvent in vacuum
waitleft a green solid, which
customwas purified by silica gel column chromatography with n-heptane/ethyl acetate

Sources & evidence

ORD record: ord-a2939614334b4eb683056687425ed5ae
Source dataset: uspto-grants-2014_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08673894B2

Reaction notes

Loading…