Categories: C-C Bond Formation > Nitrogen-containing molecules >
Synthesis of Nitro compounds by 1,4-addition
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Recent Literature
Me-DuPHOS monoxide is a very effective ligand in the enantioselective
copper-catalyzed enantioselective addition of dialkylzinc reagents to
β-nitroalkenes offering high yields of nitroalkanes, broad and complementary
substrate scope, and high enantioselectivities.
A. Côté, V. N. G. Lindsay, A. B. Charette, Org. Lett., 2007,
9, 85-87.
iPr-IsoQuinox as a chiral ligand enables a palladium-catalyzed asymmetric
addition of arylboronic acids to nitrostyrene in MeOH as solvent under an air
atmosphere providing chiral diarylsubstituted products in high yields with good
enantioselectivities. A broad range of substrates can be used.
Q. He, F. Xie, G. Fu, M. Quan, C. Shen, G. Yang, I. D. Gridnev, W. Zhang, Org. Lett.,
2015,
17, 2250-2253.
An efficient enantioselective addition of an array of arylboronic acids to
various β-nitrostyrenes is catalyzed by a novel and reactive rhodium-diene
catalyst and provides β,β-diarylnitroethanes in very good yields with excellent
enantioselectivities. Additions to 2-heteroarylnitroolefins and
2-cycloalkylnitroolefins similarly provide the desired products with high
enantioselectivities and yields.
K.-C. Huang, B. Gopula, T.-S. Kuo, C.-W. Chiang, P.-Y. Wu, J. P. Henschke,
Hsyueh-Liang Wu, Org. Lett., 2013,
15, 5730-5733.
In an efficient rhodium/olefin-sulfoxide catalyzed asymmetric conjugate
addition of organoboronic acids to nitroalkenes, 2-methoxy-1-naphthyl sulfinyl
functionalized olefin ligands are highly effective and applicable to a broad
scope of aryl, alkyl, and heteroaryl nitroalkenes.
F. Xue, D. Wang, X. Li, B. Wan, J. Org. Chem., 2012,
77, 3071-3081.
Enantioselective organocatalytic Michael addition of aldehydes to
nitroethylene catalyzed by (S)-diphenylprolinol silyl ether provides
β-substituted-δ-nitroalcohols in nearly optically pure form. The Michael adducts
bear a single substituent adjacent to the carbonyl and can be efficiently
converted to protected γ2-amino acids.
Y. Chi, L. Guo, N. A. Kopf, S. H. Gellman, J. Am. Chem. Soc., 2008,
130, 5048-5049.
Kinetic studies on enamine catalysis provided insight into the rate determining
step(s) of conjugate addition reactions between aldehydes and nitroolefins. Not
enamine formation but both the reaction of the enamine with the electrophile and
hydrolysis of the resulting imine are rate limiting. These results enabled the
reduction of the loading of the peptidic catalyst by a factor of 10.
M. Wiesner, G. Upert, G. Angelici, H. Wennemers, J. Am. Chem. Soc., 2010,
132, 6-7.
A simple, practical, and environmentally benign asymmetric Michael addition of
aldehydes to nitroolefins on water provided Michael adducts in excellent
diastereo- and enantioselectivities in the presence of a water-soluble
organocatalyst. The catalyst can be recycled for more than six times without a
significant loss of activity and stereochemical control.
Z. Zheng, B. L. Perksin, B. Ni, J. Am. Chem. Soc., 2010,
132, 50-51.
A strategy for the asymmetric Michael addition of aldehydes to nitroolefins with
a catalytic system of an organocatalyst in combination with
ionic-liquid-supported benzoic acid gives excellent diastereo- and
enantioselectivities. A notable feature of this organocatalytic system is that
the catalyst can be recycled more than 12 times without significant loss of
enantioselectivity.
D. Sarkar, R. Bhattarai, A. D. Headley, B. Ni, Synthesis, 2011,
1993-1997.
The peptide H-D-Pro-Pro-Glu-NH2 is a highly effective catalyst for
conjugate addition reactions between aldehydes and nitroethylene to obtain
γ-nitroaldehydes and, after reduction, monosubstituted γ-nitroalcohols in
excellent yields and optical purities. The products can be readily converted
into γ2-amino acids that were previously only accessible by the use
of chiral auxiliaries.
M. Wiesner, J. D. Revell, S. Tonazzi, H. Wennemers, J. Am. Chem. Soc., 2008,
130, 5610-5611.
A simple organocatalyst provided access to Michael adducts of the addition of
nitroalkenes to aldehydes with very high diastereo- and enantioselectivity and a
broad range of β-substitution patterns. Almost equimolar amounts of
the aldehyde donor can be employed.
C. Palomo, S. Vera, A. Mielgo, E. Gómez-Bengoa, Angew. Chem. Int. Ed., 2006,
45, 5984-5987.
Under the catalysis of a thiophosphoramide derived from
1,2-diphenylethane-1,2-diamine, adducts from the asymmetric Michael addition of
acetone to both aromatic and aliphatic nitroolefins were obtained in high yields
with excellent enantioselectivities under mild reaction conditions. Moreover,
the catalyst could be recovered via simple phase separation and reused at least
five times.
A. Lu, T. Liu, R. Wu, Y. Wang, G. Wu, Z. Zhou, J. Fang, C. Tang, J. Org. Chem., 2011,
76, 3872-3879.
A bifunctional organocatalyst efficiently catalyzed not only enantioselective
conjugate addition of aromatic ketones to nitroolefins in good yields with
excellent enantioselectivities but also enantioselective conjugate addition of
acetone to nitroolefins in excellent yields with high enantioselectivities.
Z.-W. Sun, F.-Z. Peng, Z.-Q. Li, L.-W. Zhou, S.-X. Zhang, X. Li, Z.-H. Shao, J. Org. Chem., 2012,
77, 4103-4110.
Copper-catalyzed conjugate addition of dialkylzing reagents to acyclic
nitroalkenes using a chiral phosphoramidite ligand gave products in
enantioselectivities up to 98%. Routes to (functionalized) 2-amino
aldehydes, acids, and alcohols are described.
A. Duursma, A. J. Minnaard, B. L. Feringa, J. Am. Chem. Soc., 2003,
125, 3700-3701.
Pyrrolidine-based chiral ionic liquids are highly efficient organocatalysts
for Michael additions of a broad range of michael donors (both ketones and
aldehydes) to nitroolefins with high yields, excellent enantioselectivities,
and very good diastereoselectivities. The ionic liquid moiety not only acts
as a tag to facilitate recycling but functions also as an efficient
chiral-induction group.
S. Luo, X. Mi, L. Zhang, S. Liu, H. Xu, J.-P. Cheng, Angew. Chem. Int.
Ed., 2006,
45, 3093-3097.
Bromide-nickel diimine complexes catalyze asymmetric Michael addition in low
yields and ee, but activation with fluoride ions leads to a significant
improvement in catalyst performance. The developed approach was applied to
the preparation of several enantioenriched GABA analogues.
O. I. Afanasyev, F. S. Kliuev, A. A. Tsygankov, Y. V. Nelyubina, E. Gutsul,
V. V. Novikov, D. Chusov, J. Org. Chem., 2022, 87,
12182-12195.
A bifunctional organocatalyst enables a 1,3-addition of silyl-dienol ethers to
nitroalkenes to provide Rauhut-Currier type products with tri- and
tetrasubstituted double bonds. The process takes place under smooth, nonanionic
conditions, and with high enantiomeric excess. A rational mechanistic pathway is
presented based on DFT and mechanistic experiments.
M. Frias, R. Mas-Ballesté, S. Arias, C. Alvarado, J. Alemán, J. Am. Chem. Soc., 2017,
139, 672-679.
An efficient and highly enantioselective conjugate addition of alkylzinc
reagents to various cyclic nitroalkenes is promoted in the presence of 0.5-5
mol % (CuOTf)2ˇC6H6 and 1-10 mol % of
chiral amino acid-based phosphine ligands at 0°C in toluene. Depending on
the reaction conditions used, either the nitro or the corresponding
α-substituted ketone product can be accessed.
C. A. Luchaco-Cullis, A. H. Hoveyda, J. Am. Chem. Soc., 2002,
124, 8192-8193.
Pyrrolidinine-thioxotetrahydropyrimidinone derivatives were tested for their
catalytic properties in various asymmetric organic transformations. These
catalysts could efficiently catalyze the reactions in brine, without the use of
organic solvent, and by employing an almost stoichiometric amount of reagents.
Thus, the products were isolated by simple extractions in excellent yields,
diastereoselectivities, and enantioselectivities.
N. Kaplaneris, G. Koutoulogenis, M. Raftopoulou, C. G. Kokotos, J. Org. Chem.,
2015,
80, 5464-5473.
A fluorous (S)-pyrrolidine sulfonamide organocatalyst promotes highly
enantio- and diastereoselective Michael addition reactions of ketones and
aldehydes with nitroolefins in water. The organocatalyst is conveniently
recovered from the reaction mixtures by fluorous solid-phase extraction and
can be reused.
L. Zu, J. Wang, H. Li, W. Wang, Org. Lett.,
2006, 8, 3077-3079.