Categories: C-C Bond Formation > Nitrogen-containing molecules >
Synthesis of Nitriles (cyanation)
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Name Reactions
Recent Literature
Nucleophilic fluorination using CsF or alkali metal fluorides was completed in
short reaction time in the presence of [bmim][BF4] affording the
desired products without any byproducts. Facile nucleophilic substitutions such
as halogenations, acetoxylation, nitrilation, and alkoxylations in the presence
of ionic liquids provided the desired products in good yields.
D. W. Kim, C. E. Song, D. Y. Chi, J. Org. Chem.,
2003, 68, 4281-4285.
Tosylmethyl isocyanide allows an efficient conversion of ketones into
nitriles by adding one carbon unit to a ketone without formation of an α-hydroxy group.
The synthesis of nitriles is applicable to a broad range of ketones.
O. H. Oldenziel, D. Van Leusen, A. M. Van Leusen, J. Org. Chem.,
1977,
42, 3114-3118.
Hydroboration with catecholborane, followed by treatment with easily
available reagents such as alkenyl sulfones or alkynyl phenyl sulfones in
the presence of a radical initiator, represents an effective and simple
one-pot procedure for direct vinylation, formylation, and cyanation.
A.-P. Schaffner, V. Darmency, P. Renaud, Angew. Chem. Int. Ed.,
2006,
45, 5847-5849.
A
direct cyanation of benzylic alcohols with TMSCN under the catalysis of
5-10 mol % of InBr3 allows the synthesis of the corresponding
nitriles in short reaction time with good yields.
G. Chen, Z. Wang, J. Wu, K. Ding, Org. Lett.,
2008,
10, 4573-4576.
A facile and efficient 1,4-addition of Me3SiCN to enones has been
achieved with perfect regioselectivity using Cs2CO3 as
catalyst in the presence of H2O as an additive. β-Cyanoketones are
obtained in excellent yields within one to five hours. Both aromatic and
aliphatic enones are suitable substrates.
J. Yang, Y. Shen, F.-X. Chen, Synthesis, 2010,
1325-1333.
An efficient 1,4-addition of TMSCN to aromatic enones has been achieved in
excellent yields in the presence of CsF as catalyst and H2O as an
additive in refluxing dioxane.
J. Yang, Y. Wang, S. Wu, F.-X. Chen, Synlett, 2009,
3365-3367.
Gd(OTf)3 as co-catalyst dramatically accelerated a Ni-catalyzed
conjugate addition of cyanide to enones. The substrate scope of the reaction is
broad, including cyclic, linear, branched, and aromatic enones. Gadolinium
triflate is supposed to facilitate the oxidative addition of Ni(0) to enones,
which constitutes a key step in the catalytic cycle.
Y. Tanaka, M. Kanai, M. Shibasaki, Synlett, 2008, 2295-2298.
A procedure for a Cu-catalyzed hydrocyanation of α-aryl diazoesters using
acetone cyanohydrin as a source of hydrogen cyanide is significantly accelerated
by addition of trimethylsilyl cyanide (TMSCN) presumably by delivering free
cyanide ion in situ. This method provides various types of α-aryl cyanoacetates
in good yields under mild conditions.
E. J. Park, S. Lee, S. Chang, J. Org. Chem., 2010,
75, 2760-2762.
A (Salen)Al-Cl complex catalyzes the asymmetric conjugate addition of
hydrogen cyanide to α,β-unsaturated imides in high yields and
enantioselectivities. The cyanide adducts can readily be converted into a
variety of useful chiral building blocks, including α-substituted-β-amino
acids.
G. M. Sammis, E. N. Jacobsen, J. Am. Chem. Soc., 2003,
125, 4442-4443.
A clean and efficient method for the oxidative transformations of primary
carboxamides to one-carbon dehomologated nitriles using the combination of
o-iodoxybenzoic acid and tetraethylammonium bromide exhibits a broad scope and
is expected to be of great utility in organic synthesis.
D. S. Bhalarao, U. S. Mahajan, K. H. Chaudhari, K. G. Akamanchi, J. Org. Chem., 2007,
72, 662-665.
