Categories: C-N Bond Formation > Amines >
Synthesis of β-Amino ketones, esters, nitriles and related compounds
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An efficient and very simple conjugate addition of aromatic and aliphatic
amines to α,β-unsaturated carbonyl compounds under solvent-free conditions in
the presence of catalytic amount of silicon tetrachloride gave the corresponding
Michael adducts with very good yields.
N. Azizi, R. Baghi, H. Ghafuri, M. Boloutchian, M. Hashemi, Synlett, 2010,
379-382.
Ceric ammonium nitrate efficiently catalyzes the aza-Michael reaction of amines
with α,β-unsaturated carbonyl compounds in water to produce the corresponding
β-amino carbonyl compounds in very good yields under mild conditions. The
reaction is procedurally simple and offers limited chemoselectivity, as aromatic
amines were found to be unreactive.
R. Varala, N. Sreelatha, S. R. Adapa, Synlett, 2006,
1549-1553.
The
addition of primary and secondary amines to α,β-unsaturated esters,
nitriles, amides, and ketones mediated by solid lithium perchlorate gave the
corresponding saturated amines under solvent-free and environmentally
friendly conditions at room temperature.
N. Azizi,
M. R. Saidi, Tetrahedron, 2004, 60, 383-387.
Cellulose-supported copper(0) efficiently catalyzes aza-Michael reactions of
N-nucleophiles, such as amines and imidazoles with α,β-unsaturated compounds to
produce the corresponding β-amino compounds and N-substituted imidazoles in
excellent yields. The recovered catalyst can be used for several cycles with
consistent activity.
K. R. Reddy, N. S. Kumar, Synlett, 2006,
2246-2250.
A mild palladium-catalyzed conjugate addition of a carbamate nucleophile to an
enone provides β-amido ketones in very good yields. The regiocontrol, neutral
conditions, and lack of preactivation of the nucleophile are attractive features
of this transformation.
M. J. Gaunt, J. B. Spencer,
Org. Lett., 2001, 3, 25-28.
A highly efficient and mild conjugate addition reaction of
aromatic amines and aromatic aza-heterocycles to α,β-unsaturated olefins is promoted by 3-7 mol % of a Cu complex
generated in situ from a mixture of inexpensive CuCl, a readily available
phosphine or imidazolium salt, and KOtBu at ambient temperature. A wide range
of β-amino sulfone, β-amino nitrile, and β-amino carbonyl compounds is selectively synthesized in high yields.
S. Kim, S. Kang, G. Kim, Y. Lee, J. Org. Chem.,
2016,
81, 4048-4057.
The use of readily available and stable Weinreb amides enables a mild and
efficient sequential synthesis of β-aminoketones or their derivatives ( e.g.,
pyrazolines). The reaction proceeds in good to excellent yields for a variety of amides, vinyl Grignard reagents and N-nucleophiles.
A. Gomtsyan, R. J. Koenig, C.-H. Lee, J. Org. Chem., 2001,
66, 3613-3616.
A sequential nucleophilic substitution at the carbonyl group of amides by
vinylmagnesium bromide followed by Michael reaction after quench by water
provides β-aminoketones.
A. Gomtsyan,
Org. Lett., 2000, 2, 11-13.
A gold-catalyzed hydroamination of propargylic
alcohols with anilines provides 3-hydroxyimines. A subsequent reduction gives
1,3-amino alcohols with high syn selectivity. By using a
catalytic amount of aniline, 3-hydroxyketones can be obtained in high yield
directly from propargylic alcohols. And a selective formation of 3-aminoketones via a rearrangement/hydroamination
pathway is also described.
V. Laserna, M. J. Porter, T. D. Sheppard, J. Org. Chem., 2019,
84, 11391-11406.
1,4-diazobicyclo[2.2.2]octane (DABCO) based ionic liquids were used as
recyclable catalysts for the aza-Michael addition at room temperature without
any organic solvent. A low loading of the very efficient [DABCO-PDO][OAc]
catalyzed reactions of various amines with a wide range of α,β-unsaturated
amides to afford products in very good yields within hours. Moreover, the
catalyst could be reused up to eight times.
A. Ying, Z. Li, J. Yang, S. Liu, S. Xu, H. Yan, C. Wu, J. Org. Chem., 2014,
79, 6510-6516.
A highly enantio- and regioselective Ni-catalyzed hydroamination of readily
available unactivated alkenes bearing weakly coordinating native amides or
esters provides β- or γ-amino acid derivatives and 1,2- or 1,3-diamines for both
terminal and internal unactivated alkenes and a broad amine coupling partner
scope. The mild reaction is well suited for late-stage
functionalization.
C. Lee, H.-J. Kang, H. Seo, S. Hong, J. Am. Chem. Soc.,
2022, 144, 9091-9100.
The efficiency of a CeCl3·7H2O-NaI system supported on
silica gel in conjugate addition of secondary amines to α,β-enones is remarkable: no inert conditions are required, since oxygen and moisture are tolerated.
The mildness of the reaction conditions and simplicity of operation make the
reaction highly synthetically useful.
G. Bartoli, M. Bosco, E. Marcantoni, M. Petrini, L. Sambri, E. Torregiani, J. Org. Chem., 2001,
66, 9052-9055.
CeCl3 • 7H2O/NaI supported on
neutral alumina (Al2O3) promotes heteroatom Michael
additions under solvent-free conditions. The CeCl3 • 7H2O/NaI/Al2O3
system works well for hetero-Michael additions of weak nucleophiles such as
imidazoles and carbamates to various acceptors.
G. Bartoli, M. Bartolacci, A. Giuliani, E. Marcantoni, M. Massaccesi, E.
Torregiani, J. Org. Chem., 2005,
70, 169-174.
G. Bartoli, M. Bartolacci, A. Giuliani, E. Marcantoni, M. Massaccesi, E.
Torregiani, J. Org. Chem., 2005,
70, 169-174.
A versatile RuCl3-catalyzed 1,4-conjugate addition of primary,
secondary and aromatic amines, thiols, and carbamates to α,β-unsaturated
compounds in poly(ethylene glycol) (PEG) provides the desired β-substituted
carbonyls in high yields. RuCl3-PEG offers low sensitivity toward moisture and
oxygen, high tolerance of different functional groups, and efficient
recyclability.
H. Zhang, Y. Zhang, L. Liu, H. Xu, Y. Wang, Synthesis, 2005,
2129-2136.
A copper-catalyzed electrophilic amination of cyclopropanols with O-benzoyl-N,N-dialkylhydroxylamines
enables the synthesis of various β-aminoketones via C-C bond cleavage and Csp3-N
bond formation. The mild reaction conditions tolerate several functional groups
including benzoate, tosylate, expoxide, and α,β-unsaturated carbonyls.
Z. Ye, M. Dai, Org. Lett.,
2015,
17, 2190-2193.
In a palladium-catalyzed intermolecular aminocarbonylation of alkenes, the use
of hypervalent iodine reagent can accelerate the reaction. The current
transformation presents a convenient method to generate β-amino acid derivatives
from simple alkenes.
J. Cheng, X. Qi, M. Li, P. Chen, G. Liu, J. Am. Chem. Soc., 2015,
137, 2480-2483.
A general alkylamination of vinylarenes and an unprecedented
diastereoselective anti-carboamination of unsaturated esters provide amines
and unnatural β-amino acids. This alkylamination is enabled by an iron catalyst
and alkyl diacyl peroxides, that serve as both alkylating reagents and internal
oxidizing agents.
B. Qian, S. Chen, T. Wang, X. Zhang, H. Bao, J. Am. Chem. Soc., 2017,
139, 13076-13082.
A combined amino- and N-heterocyclic carbene (NHC)-catalyzed one-pot
reaction sequence using commercially available catalysts at low catalyst
loadings gives β-hydroxy and β-amino esters in high yield and excellent
enantiopurity. The generation of quaternary stereocenters and application in
gram-scale synthesis were also realized, with no requirements of inert or
anhydrous reaction conditions.
H. Jiang, B. Gschwend, Ł. Albrecht, K. A. Jørgensen, Org. Lett., 2010,
12, 5052-5055.
The regio- and stereoselective aminochlorination of α,β-unsaturated ketones
with N,N-dichloro-p-toluenesulfonamide (4-TsNCl2) and
CuOTf as catalyst provides an easy access to
vicinal haloamino ketones, with excellent regioselectivity and good yields.
Aromatic and aliphatic enones give opposite regioselectivity.
D. Chen, C. Timmons, S. Chao, G. Li, Eur. J. Org. Chem., 2004,
3097-3101.