Categories: C-N Bond Formation > Amines >
Synthesis of primary amines
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Name Reactions
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Mitsunobu Reaction |
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Staudinger Reaction |
Recent Literature
Treatment of ketones with
ammonia in ethanol and titanium(IV) isopropoxide, followed by in situ reduction
with sodium borohydride allows a highly chemoselective reductive
mono-alkylation of ammonia. A simple workup afforded primary amines in good to
excellent yields. Reductive alkylation of ammonia with aldehydes afforded the corresponding symmetrical secondary amines selectively.
B. Miriyala, S. Bhattacharyya, J. S. Williamson, Tetrahedron, 2004,
60, 1463-1471.
By optimizing the metal hydride/ammonia mediated reductive amination of
aldehydes and hemiacetals, primary amines were selectively prepared with no or
minimal formation of the usual secondary and tertiary amine byproduct. The
methodology was performed on a range of functionalized aldehyde substrates,
including in situ formed aldehydes from a Vasella reaction.
E. M. Dangerfield, C. H. Plunkett, A. L. Win-Mason, B. L. Stocker, M. S. M.
Timmer, J. Org. Chem., 2010,
75, 5470-5477.
Cp*Ir complexes bearing a 2-picolinamide moiety effectively catalyze a direct
reductive amination of ketones to give primary amines under transfer
hydrogenation conditions using ammonium formate as both the nitrogen and
hydrogen source.
K. Tanaka, T. Miki, K. Murata, A. Yamaguchi, Y. Kayaki, S. Kuwata, T. Ikariya,
M. Watanabe, J. Org. Chem., 2019,
84, 10962-10977.
An efficient, metal and base-free, chemoselective reaction of boronic acids with
cyanamidyl/arylcyanamidyl radicals provides primary aryl-, heteroaryl-, and
alkyl amines at ambient temperature within 1 h. The reaction is mediated by PIFA
and NBS.
N. Chatterjee, M. Arfeen, P. V. Bharatam, A. Goswami, J. Org. Chem.,
2016,
81, 5120-5127.
A bench-stable NH-oxaziridine reagent enables a primary electrophilic
amination of primary, secondary, and tertiary organometallic substrates. This
facile and highly chemoselective transformation occurs in a single step without
transition metal catalysts at ambient temperature. A convenient extractive
work-up provides alkylamine products.
N. E. Behnke, R. Kielawa, D.-H. Kwon, D. H. Ess, L. Kürti, Org. Lett.,
2018, 20, 8064-8068.
In the presence of 2-amino-2-phenylpropanoate salts as the amine source,
aromatic aldehydes underwent an efficient decarboxylative transamination under
very mild conditions to produce a variety of arylmethylamines in very good
yields.
W. Cai, Y. Yang, J. Ma, J. Cao, X. Ren, B. Zhao, Org. Lett., 2023, 25,
3876-3880.
The use of aqueous ammonia is essential for a palladium-catalyzed allylic
amination for the preparation of primary amines. It is noteworthy that ammonia
gas did not react at all. The first catalytic asymmetric synthesis using aqueous
ammonia as a nitrogen source has also been demonstrated.
T. Nagano, S. Kobayashi, J. Am. Chem. Soc., 2008,
131, 4200-4201.
An experimentally simple Microwave-assisted reductive alkylation of methyl
carbamate with a range of aldehydes provides, after basic work-up, structurally
diverse primary amines. This method is particularly amenable to high-throughput
synthesis.
F. Lehmann, M. Scobie, Synthesis, 2008,
1679-1681.
The synthesis of free α-chiral amines by a one-pot multicomponent procedure
involves the formation of N-diphenylphosphinoylimines from
commercially available starting materials and the subsequent
enantioselective addition of diakylzinc reagents using an air-stable
precatalyst complex.
Cote, A. B. Charette, J. Org. Chem., 2005, 70, 10864-10867.
An oxime reagent as an amino group source achieves a direct conversion from
acetyl arenes and alkanes to primary amines with C-C bond cleavage via domino
transoximation/Beckmann rearrangement/Pinner reaction. The method was also
applied to the synthesis of γ-aminobutyric acids, such as rolipram and baclophen.
K. Hyodo, G. Hasegawa, H. Maki, K. Uchida,
Org. Lett., 2019, 21, 2818-2822.
An electrophilic amination of Grignard reagents with
4,4,5,5-tetramethyl-1,3-dioxolan-2-one O-phenylsulfonyloxime followed by
acidic hydrolysis of the resulting imines gives primary amines.
M. Kitamura, T. Suga, S. Chiba, K. Narasaka, Org. Lett.,
2004,
6, 4619-4621.
Cp*Ir complexes bearing a chiral N-(2-picolyl)sulfonamidato catalyze a
convenient asymmetric reductive amination of benzylic ketones using readily
available β-amino alcohols as chiral aminating agents. The amino alcohol-derived
chiral auxiliary was easily removed by mild periodic oxidants, leading to
optically active primary β-arylamines without erosion of the optical purity.
T. Kawada, K. Yabushita, T. Yasuda, T. Ohta, T. Yajima, K. Tanaka, N. Utsumi, M.
Watanabe, K. Murata, Y. Kayaki, S. Kuwata, T. Katayama, J. Org. Chem., 2022, 87,
8458-8468.
A chiral pyridoxamine catalyzes an asymmetric biomimetic transamination of
trifluoromethyl ketones with 2,2-diphenylglycine as the amine source to produce
optically active α-trifluoromethyl amines in very good yields with excellent
ee's under mild conditions.
W. Cai, D. Cai, H. Liang, X. Ren, B. Zhao, J. Org. Chem., 2023, 88,
7849-7857.
(NaN(SiMe3)2) catalyzes a deprotonation of allylbenzenes. Trapping of the deprotonated allyl anion with in situ generated N-(trimethylsilyl) aldimines provides
value-added homoallylic amines with excellent linear
selectivity.
Y. Gu, Y.-E. Wang, Y. Yuan, H. Xu, Y. Lu, Y. Zhang, F. Xue, D. Xiong, J. Mao, J. Org. Chem., 2023, 88,
7362-7372.
Related
A photoredox catalyzed, thiyl-radical mediated, reversible hydrogen atom
transfer enables a stereoselective α-amino C-H epimerization of exocyclic amines
to provide thermodynamically controlled anti:syn isomer ratios. The method is
applicable to different substituents and substitution patterns.
M. Vargas-Rivera, A. S. Liu, J. A. Ellman, Org. Lett., 2023, 25,
9197-9201.