Categories: C-C Bond Formation > Nitrogen-containing molecules >
Synthesis of α-Aminonitriles
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Name Reactions
Recent Literature
S-oxidation of potassium thiocyanate releases cyanide units that can be
trapped in the presence of co-oxidized tertiary amines to form α-amino nitriles.
These cyanations work in aqueous solutions without catalyst and without toxic
byproducts.
A. Wagner, A. R. Ofial, J. Org. Chem.,
2015,
80, 2848-2854.
A mild protocol for the α-C-H cyanation of tertiary aliphatic, benzylic,
and aniline-type substrates and complex substrates tolerates a broad range of
fuctional groups, including various heterocycles and ketones, amides, olefins,
and alkynes. The presented catalyst system especially tolerates functional
groups that typically react with free radicals, suggesting an alternative
reaction pathway.
O. Yilmaz, C. Dengiz, M. H. Emmert, J. Org. Chem., 2021, 86,
2489-2498.
RuCl3-catalyzed oxidative cyanation of tertiary amines with sodium
cyanide under molecular oxygen at 60°C gives the corresponding α-aminonitriles
in excellent yields. This reaction is clean and should be an environmentally
benign and useful process.
S.-I. Murahashi, N. Komiya, H. Terai, T. Nakae, J. Am. Chem. Soc.,
2003,
125, 15312-15313.
A novel, simple and efficient one-pot synthesis of α-aminonitriles has been
achieved by a three-component condensation of carbonyl compounds, amines and
trimethylsilyl cyanide in the presence of (bromodimethyl)sulfonium bromide
as a catalyst at room temperature.
B. Das, R. Ramu, B. Ravikanth, K. Ravinder Reddy,
Synthesis, 2006, 1419-1422.
An environmentally benign and highly efficient, biomimetic procedure for the
nucleophilic addition of trimethylsilyl cyanide to imines (Strecker reaction)
using β-cyclodextrin as a catalyst and water as solvent afforded
α-aminonitriles in quantitative
yields. The catalyst can be recycled a number of times without loss in activity.
K. Surendra, N. S. Krishnaveni, A. Mahesh, K. R. Rao, J. Org. Chem., 2006,
71, 2532-2534.
A very fast, simple one-step, environmentally friendly procedure for the synthesis
of α-aminonitriles in high yields from aldehydes, using trimethylsilyl cyanide in
the absence of solvent, gives almost quantitative yields of
the corresponding α-aminonitriles. However, only
cyclic ketones afford the corresponding α-aminonitriles in excellent chemical
yields.
A. Baeza, C. Nájera, J. M. Sansano, Synthesis, 2007,
1230-1234.
A simple and efficient one-pot, three-component Strecker reaction of aldehydes
and ketones with aliphatic or aromatic amines and trimethylsilyl cyanide in the
presence of a palladium Lewis acid catalyst allows the synthesis of
α-aminonitriles in good yields at room temperature.
J. Jarusiewicz, Y. Choe, K. Soo. Yoo, C. P. Park, K. W. Jung, J. Org. Chem., 2009,
74, 2873-2876.
After an iridium-catalyzed reduction of secondary amides, the resulting
imines can undergo the Strecker reaction, the Mannich reaction, allylation, and
[3 + 2]-cycloaddition. The method shows high chemoselectivity in the presence of
other functional groups such as methyl ester.
Y. Takahashi, R. Yoshii, T. Sato, N. Chida, Org. Lett.,
2018, 20, 5705-5708.
A highly enantioselective cyanation of imines at room temperature in the
presence of 5 mol% of a partially hydrolyzed titanium alkoxide (PHTA)
precatalyst together with a readily available N-salicyl-β-aminoalcohol
ligand gives aminonitriles with up to 98% ee and quantitative yields in 15 min
of reaction time. Various N-protecting groups are tolerated.
A. M. Seayad, B. Ramalingam, K. Yushinaga, T. Nagata, C. L. L. Chai, Org. Lett., 2010,
12, 264-267.
An efficient, safe, and environmentally friendly TBHP-mediated rearrangement
of aryl/alkylidene malononitrile with anilines produces in situ HCN as the
cyanide source for the synthesis of substituted α-aminonitriles and
α-aminoamides in very good yields. This method features good functional group
tolerance, and the in situ-generated HCN bypasses the use of an external cyanide
source.
S. P. Bhoite, A. H. Bansode, G. Suryavanshi, J. Org. Chem., 2020, 85, 14858-14865.
An indium-catalyzed three-component coupling reaction of alkynes, amines, and
trimethylsilyl cyanide provides quaternary α-aminonitrile derivatives via
hydroamination of the alkyne and a subsequent nucleophilic addition of Me3SiCN.
Y. Hamachi, M. Katano, Y. Ogiwara, N. Sakai, Org. Lett., 2016, 18,
1634-1637.
An aluminum complex was found to be high yielding and enantioselective for
the addition of cyanide to aldimines and ketimines. The present catalyst
provides uniformly high enantioselectivity for aromatic, heteroaromatic, and
aliphatic aldimines and ketimines using ethyl cyanoformate as the cyanide source.
J. P. Abell, H. Yamamoto, J. Am. Chem. Soc., 2009,
131, 15118-15119.
An N-heterocyclic carbene as a nucleophilic organocatalyst allows the
cyanation of ketones and ketimines with TMSCN in good yields under mild
reaction conditions.
Y. Fukuda, K. Kondo, T. Aoyama,
Synthesis, 2006, 2649-2652.
Aryl imines, formed in situ from aldehydes and amines undergo mild nucleophilic addition with trimethylsilyl cyanide on the surface of montmorillonite KSF clay to afford the corresponding α-aminonitriles in excellent yields. The solid acid can be recovered and recycled in subsequent reactions with a gradual decrease of activity.
J. S. Yadav, B. V. S. Reddy, B. Eeshwaraiah, M. Srinivas, Tetrahedron,
2004, 60, 1767-1771.
Related
An oxidative Strecker reaction of aldehydes, amines, and TMSCN in a biphasic
solvent system in the presence of Oxone, TBAB and sodium bicarbonate affords
α-iminonitriles in good yields. This three component reaction is applicable to a
wide range of aldehydes and amines.
J.-B. Gualtierotti, X. Schumacher, Q. Wang, J. Zhu, Synthesis, 2013, 45,
1380-1386.
