Amination

The Gabriel reagent is widely used as a nucleophilic aminating agent since its reactivity is reliable and its handling is easy.1) Recently, a variety of aminating agents analogous to the Gabriel reagent have been reported, for example, tert-butyl methyl iminodicarboxylate, N-(tert-butoxycarbonyl)-p-toluenesulfonamide, sodium diformamide, and di-tert-butyl iminodicarboxylate.

The potassium salt of imide 1 reacts with alkyl halide to give imide 2. 2 is treated with base or acid to give either N-Boc-amine 3 or N-metoxycarbonylamine 4, respectively. Moreover, 1 also serves as an acid nucleophile in the Mitsunobu reaction to allow for the conversion of hydroxyl groups to amino groups. Therefore, 1 is a useful reagent to give mono protected amines.2)
On the other hand, acetoxime O-(2,4,6-trimethylphenyl)sulfonate 5 has been reported as a useful electrophilic aminating agent. 5 reacts with Grignard reagent in the presence of a catalytic amount of magnesium chloride to afford primary amines in good yields.3)

A1441 A1441 A1632 A1632 A1137 A1137
A1341 A1341 B2303 B2303 B1648 B1648
B2857 B2857 I0510 I0510 C1757 C1757
I0497 I0497 B1734 B1734 D2361 D2361
D1672 D1672 M1182 M1182 H0093 H0093
H0258 H0258 H0196 H0196 H0530 H0530
M0343 M0343 M0886 M0886 D1899 D1899
P1235 P1235 P0403 P0403 D2479 D2479
T1184 T1184
A1441 Acetoxime O-(2,4,6-Trimethylphenylsulfonate)
A1632 N-Allyloxycarbonyl-2-nitrobenzenesulfonamide
A1137 4-Amino-1,2,4-triazole
A1341 Azidomethyl Phenyl Sulfide
B2303 N-(tert-Butoxycarbonyl)-2-nitrobenzenesulfonamide
B1648 N-(tert-Butoxycarbonyl)-p-toluenesulfonamide
B2857 tert-Butyl [Bis(4-methoxyphenyl)phosphinyloxy]carbamate
I0510 tert-Butyl Methyl Iminodicarboxylate
C1757 N-Carbobenzoxy-2-nitrobenzenesulfonamide
I0497 Di-tert-butyl Iminodicarboxylate
B1734 Diethyl N-(tert-Butoxycarbonyl)phosphoramidate
D2361 Diethyl Phosphoramidate
D1672 Diphenylphosphoryl Azide
M1182 Ethyl O-Mesitylsulfonylacetohydroxamate [Precursor of the Powerful Aminating Reagent]
H0093 Hexamethylenetetramine
H0258 Hydroxylamine Hydrochloride
H0196 Hydroxylamine Sulfate
H0530 Hydroxylamine-O-sulfonic Acid
M0343 O-Methylhydroxylamine Hydrochloride
M0886 O-Methylhydroxylamine Hydrochloride (ca. 40% in Water, ca. 5.4mol/L)
D1899 N,O-Dimethylhydroxylamine Hydrochloride
P1235 Phthalimide DBU Salt
P0403 Phthalimide Potassium Salt
D2479 Sodium Diformylamide
T1184 Trimethylsilylmethyl Azide
Page Top

Literature

1) S. Gabriel, Ber., 1887, 20, 2224 [DOI] ; M. S. Gibson, R. W. Bradshaw, Angew. Chem., Int. Ed., 1968, 7, 919 [DOI]; U. Ragnarsson, L. Grehn, Acc. Chem. Res., 1991, 24, 285 [DOI].
2) J. D. Elliott, J. H. Jones, J. Chem. Soc., Chem. Commun., 1977, 758 [DOI]; C. T. Clarke, J. D. Elliott, J. H. Jones, J. Chem. Soc., Perkin Trans. 1, 1978, 1088 [DOI]; J. M. Chong, S. B. Park, J. Org. Chem., 1993, 58, 7300 [DOI].
3) E. Erdik, M. Ay, Synth. React. Inorg. Met.-org. Chem., 1989, 19, 663 [DOI].

Page Top
kdjoad0000003w6e