4 Experimental Data
All glassware was flame-dried before use and the reactions were performed under
an atmosphere of argon. All dry solvents were bought from Acros and used as
received. All other reagents, the synthesis of which is not described below, were
used as received from commercial suppliers. Reaction progress was monitored by
thin layer chromatography (TLC) performed on aluminum plates coated with silica gel F254 with 0.2 mm thickness. Chromatograms were visualized by fluorescence quenching with UV light at 254 nm or by staining using potassium permanganate. Column chromatography was performed using silica gel 60 (230-400
mesh, Merck and co.). Neat infra-red spectra were recorded using a Perkin-Elmer
Spectrum 100 FT-IR spectrometer. Wavenumbers (= 1/λ) are reported in cm
-1
.
Mass spectra were obtained using a Finnigan MAT 8200 or (70 eV) or an Agilent
5973 (70 eV) spectrometer, using electrospray ionisation (ESI). All
1
H NMR and
13
C NMR spectra were recorded using a Bruker AV-400, AV-600 or AV-700 spectrometer at 300K. Chemical shifts were given in parts per million (ppm, δ), referenced to the solvent peak of CDCl3, defined at δ = 7.26 ppm (
1
H NMR) and δ =
77.16 (
13
C NMR). Coupling constants are quoted in Hz (J).
1
H NMR splitting patterns were designated as singlet (s), doublet (d), triplet (t), quartet (q). Splitting
patterns that could not be interpreted or easily visualized were designated as multiplet (m).
Amides
Amides 1.1b,d,e,h–m were either generously donated by other members of our
group or received from commercial suppliers.
General procedure A for the synthesis of amides
To the a solution of the acid (1 eq.) in DCM (0.2 M) was added 1-hydroxybenzotriazole hydrate (1 eq.), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1 eq.), triethylamine (1 eq.) and the secondary amine (1 eq.). The solution
was stirred for 16 h. After dilution in AcOEt, the organic phase was washed subsequently with a solution of HCl (1 M), saturated solution of NaHCO3 and finally
with a saturated solution of NaCl. The organic layer was separated, dried over
MgSO4 and the solvent was removed under reduced pressure. The crude mixture
was purified by column chromatography on silica gel.
© The Editor(s) (if applicable) and The Author(s), under exclusive license
to Springer Fachmedien Wiesbaden GmbH, part of Springer Nature 2020
M. Lemmerer, Chemoselective Nucleophilic α-Amination of Amides,
BestMaters, https://doi.org/10.1007/978-3-658-30020-3_4
All glassware was flame-dried before use and the reactions were performed under
an atmosphere of argon. All dry solvents were bought from Acros and used as
received. All other reagents, the synthesis of which is not described below, were
used as received from commercial suppliers. Reaction progress was monitored by
thin layer chromatography (TLC) performed on aluminum plates coated with silica gel F254 with 0.2 mm thickness. Chromatograms were visualized by fluorescence quenching with UV light at 254 nm or by staining using potassium permanganate. Column chromatography was performed using silica gel 60 (230-400
mesh, Merck and co.). Neat infra-red spectra were recorded using a Perkin-Elmer
Spectrum 100 FT-IR spectrometer. Wavenumbers (= 1/λ) are reported in cm
-1
.
Mass spectra were obtained using a Finnigan MAT 8200 or (70 eV) or an Agilent
5973 (70 eV) spectrometer, using electrospray ionisation (ESI). All
1
H NMR and
13
C NMR spectra were recorded using a Bruker AV-400, AV-600 or AV-700 spectrometer at 300K. Chemical shifts were given in parts per million (ppm, δ), referenced to the solvent peak of CDCl3, defined at δ = 7.26 ppm (
1
H NMR) and δ =
77.16 (
13
C NMR). Coupling constants are quoted in Hz (J).
1
H NMR splitting patterns were designated as singlet (s), doublet (d), triplet (t), quartet (q). Splitting
patterns that could not be interpreted or easily visualized were designated as multiplet (m).
Amides
Amides 1.1b,d,e,h–m were either generously donated by other members of our
group or received from commercial suppliers.
General procedure A for the synthesis of amides
To the a solution of the acid (1 eq.) in DCM (0.2 M) was added 1-hydroxybenzotriazole hydrate (1 eq.), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1 eq.), triethylamine (1 eq.) and the secondary amine (1 eq.). The solution
was stirred for 16 h. After dilution in AcOEt, the organic phase was washed subsequently with a solution of HCl (1 M), saturated solution of NaHCO3 and finally
with a saturated solution of NaCl. The organic layer was separated, dried over
MgSO4 and the solvent was removed under reduced pressure. The crude mixture
was purified by column chromatography on silica gel.
© The Editor(s) (if applicable) and The Author(s), under exclusive license
to Springer Fachmedien Wiesbaden GmbH, part of Springer Nature 2020
M. Lemmerer, Chemoselective Nucleophilic α-Amination of Amides,
BestMaters, https://doi.org/10.1007/978-3-658-30020-3_4