Silver-promoted regio- and stereoselective aminocyanation of alkynes for the synthesis of β-aminoacrylonitriles using N-isocyanoiminotriphenylphosphorane

Article abstract of DOI:10.1016/j.tetlet.2019.05.045

The silver-promoted intermolecular aminocyanation of alkynes for the synthesis of (Z)-β-aminoacrylonitriles is reported, using N-isocyanoiminotriphenylphosphorane (NIITP) as both the nitrile and amine source. The transformation proceeds in moderate to good yields, and in a regio- and stereoselective manner, using a wide range of acetylenes.

Full text of DOI:10.1016/j.tetlet.2019.05.045

Accepted Manuscript
Silver-promoted regio- and stereoselective aminocyanation of alkynes for the
synthesis of β-aminoacrylonitriles using N-isocyanoiminotriphenylphosphor-
ane
Lingnan Chen, Shanshan Cao, Jingping Zhang, Zikun Wang
PII:
S0040-4039(19)30490-3
https://doi.org/10.1016/j.tetlet.2019.05.045
TETL 50817
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
24 April 2019
21 May 2019
23 May 2019
Please cite this article as: Chen, L., Cao, S., Zhang, J., Wang, Z., Silver-promoted regio- and stereoselective
aminocyanation of alkynes for the synthesis of β-aminoacrylonitriles using N-isocyanoiminotriphenylphosphorane,
Tetrahedron Letters (2019), doi: https://doi.org/10.1016/j.tetlet.2019.05.045
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Silver-promoted regio- and stereoselective
aminocyanation of alkynes for the synthesis
Leave this area blank for abstract info.
of
isocyanoiminotriphenylphosphorane
Lingnan Chen,a,§ Shanshan Cao,a,§Jingping Zhang*,a and Zikun Wang*,a
β-aminoacrylonitriles
using
N-

1
Tetrahedron Letters
Silver-promoted regio- and stereoselective aminocyanation of alkynes for the
synthesis of β-aminoacrylonitriles using N-isocyanoiminotriphenylphosphorane
Lingnan Chen,a,# Shanshan Cao,a,# Jingping Zhang*,a and Zikun Wang*,a
# These authors contributed equally to this work.
a Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Northeast Normal University, Changchun 130024, China.
* Corresponding author. E-mail: wangzk076@nenu.edu.cn (Z. Wang); jpzhang@nenu.edu.cn (J. Zhang).
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The silver-promoted intermolecular aminocyanation of alkynes for the synthesis of (Z)-β-
aminoacrylonitriles is reported, using N-isocyanoiminotriphenylphosphorane (NIITP) as both
the nitrile and amine source. The transformation proceeds in moderate to good yields, and in a
regio- and stereoselective manner, using a wide range of acetylenes.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Silver-promoted
aminocyanation
alkynes
N-isocyanoiminotriphenylphorane
The nitrile group is a key functionality in organic synthesis; in
addition to its presence in numerous bioactive molecules, it is a
valuable precursor to many other functional groups, such as
carbonyls and amines.1 Among various methods to access
nitriles, the direct addition of cyano groups to non-activated
carbon-carbon multiple bonds is highly appealing.2 Although
transition metal-catalyzed hydrocyanations that proceed by
cleavage of X−CN bonds (X = C, O, Si, etc.) are well-
established,3 cyanofunctionalizations that directly introduce two
functionalities across a C−C multiple bond, leading to β-
functionalized nitriles in a one-step operation, are
underdeveloped.4 Aminocyanation is a particularly attractive
example due to the synthetic utility of the resulting β-
aminonitriles and β-aminoacrylonitriles.5 However, of the few
reported examples,6 nearly all are restricted to intramolecular
processes that require complex, specialized starting materials
(Fig. 1a).6a-d To the best of our knowledge, intermolecular
aminocyanation has only been described using styrenes, with
initial work by Zhang and co-workers6e being recently followed
by a catalytic asymmetric variant from Liu and co-workers (Fig.
1b);6f moreover, these methods require two separate reagents to
provide the amino and cyano groups.6e,6f The development of
intermolecular aminocyanation of C−C multiple bonds therefore
remains a challenging task, compounded by the scarcity of
convenient aminocyanating agents.
Figure 1. Aminocyanation of C-C multiple bonds
coupling reactions,8 as carbene species in insertion reactions,9
and as 'cyano' sources for the cyanation of several functional
groups.10 Isocyanides equipped with substituents that fine-tune
their reactivity (so-called 'functionalized' isocyanides)11 occupy a
privileged position in terms of synthetic utility. NIITP, a
Herein, we describe the first intermolecular aminocyanation of
simple alkynes, in which the readily available isocyanide
N-isocyanoiminotriphenylphosphorane (NIITP) serves as a
source of both the amine and nitrile components (Fig. 1c).
Isocyanides are versatile synthetic intermediates with various
applications,7 serving as key ingredients in multicomponent
functionalized isocyanide that is comparatively underexploited
aside from its use as a 'CNN' building block in base-mediated
heterocycle synthesis,12 is synthetically attractive as a stable, safe,
easy-to-handle, and odorless solid isocyanide.13 Building on our

2
Tetrahedron
Scheme 1. Aminocyanation reaction scope.a,b
exploration of the silver-catalyzed σ-activation of isocyanides14
and alkynes,15 we questioned whether NIITP could affect
intermolecular alkyne aminocyanation, thereby providing a novel
and practical route to β-aminoacrylonitriles. This would not only
represent the first intermolecular aminocyanation reaction of
alkynes,6 and the first intermolecular aminocyanation of any kind
that uses a single amine/CN source, but also the first exploitation
of NIITP in a transition metal-catalyzed transformation.11,12
Table 1. Optimization of the reaction conditions.a
Entry [Ag] (mol%)
Solvent
Yieldb 3a
22%
21%
18%
trace
trace
trace
trace
trace
53%
trace
trace
18%
31%
26%
trace
trace
1
Ag2CO3 (30%)
AgF (30%)
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
Toluene
2
3
AgS2O4 (30%)
AgOAc (30%)
Ag2O (30%)
4
5
6
Ag3PO4 (30%)
AgOTf (30%)
AgBF4 (30%)
Ag2CO3 (50%)
Ag2CO3 (100%)
Ag2CO3 (50%)
Ag2CO3 (50%)
Ag2CO3 (50%)
Ag2CO3 (50%)
Ag2CO3 (50%)
Ag2CO3 (50%)
7
8
a Reagents and conditions:
1 (1.0 mmol), 2 (2.0 mmol), Ag2CO3
9c
10d
11e
12
13
14
15
16
(50 mol%), H2O (2.0 equiv.), 1,4-dioxane (5 mL), 70 °C, under
N2, 10 h. Isolated yields. b The Z/E ratio of products was
characterized by 1H NMR spectroscopy of the reaction system.
We next set out to investigate the scope of the reaction. A
variety of aryl acetylenes were found to react efficiently
with NIITP to afford the corresponding β-
aminoacrylonitriles 3b-p with excellent regio- and
stereoselectivity (Scheme 1). Substituent variation on the
aryl acetylene had little effect on the reaction: electron-
THF
CH3CN
DMSO
DMF
neutral (1b), electron-donating (1c
1g 1h), and halogens (1i 1j) were all well tolerated, with
the desired products 3b isolated in 31–75% yield;
particular notable is the compatibility with ortho
substituents (1f, 1h). Whereas substrates with strong
electron-withdrawing groups (such as an ester, 1k) were not
-f), electron-withdrawing
a Reagents and conditions: 1a (1.0 mmol), 2 (2.0 mmol), Ag2CO3,
H2O (2.0 equiv.), solvent (5 mL), 70 °C, under N2, 10 h. b Isolated
yield. c Byproducts were isolated and identified as 4a (16%) and 5a
(10%). d 5a was obtained in 53% yield. e Without H2O.
(
,
,
-
j
At the onset of this work, we were pleased to find that alkyne
1a indeed underwent aminocyanation with NIITP (2) to give
β-aminoacrylonitrile 3a, in the presence of 30 mol% of various
silver salts and 2 equiv. of H2O at 70 °C in 1,4-dioxane (Table 1).
In contrast, other reported aminocyanation sources, such as
NFSI/TMSCN6e,f and Ph(Ts)N–CN (NCTS),16 did not afford the
desired products. Ag2CO3 was found to be the most suitable
promoter for this process, giving 3a in 22% yield (Entry 1). AgF
and Ag2SO4 also proved effective (Entries 2 and 3), in contrast to
other silver salts, such as AgOAc, Ag2O, Ag3PO4, AgOTf and
AgBF4 (Entries 4–8). An increase in the loading of Ag2CO3 to 50
mol% significantly improved the yield to 53% (Entry 9), with
byproducts 3-(p-tolyl)propiolonitrile (4a, 16%) and 3-p-tolyl-1H-
pyrazole (5a, 10%) also observed. Further increasing the amount
of the silver salt proved detrimental, with only trace amounts of
3a isolated using a stoichiometric amount of Ag2CO3 (Entry 10).
The reason for this is that an excess of Ag2CO3 can increase the
pH value of the solution which promotes the hydrolysis of
intermediate II to give compound 5a (Fig. 2). A control
suitable, disubstituted aryl acetylenes (1l
desired products (3l ). Biphenyl (1o) and naphthyl (1p
acetylenes also gave the corresponding aminoacrylamides
3o and 3p, 66% and 48% yield, respectively). Furthermore,
the structure of 3o was confirmed by X-ray single crystal
diffraction (CCDC 1556439).
-n) provided the
-
n
)
(
The scalability of this protocol was evaluated using the
reaction of phenylacetylene (1b) with NIITP on a 20 mmol scale.
Product 3b was obtained in 55% yield (1.58 g, see Scheme 2),
which is consistent with the result on a 1 mmol scale.
The synthetic utility of 3b was explored in a range of
derivatization reactions, including conversion into aniline 6a
(71%), reduction to β-aminonitrile 6b (61%), and enamine
hydrolysis to β-ketonitrile 6c (83%). More complex
transformations such as perbromination to bromoimine 6d (68%),
and oxidative dimerization/cyclization with potassium persulfate
to the tetrasubstituted 2,4-dihydro-pyrrole 6e (57%) also
proceeded with high efficiency. Further oxidative ring-forming
reactions were performed, including the reaction of 3b with
phenylacetylene to give aminonaphthalene 6f (55%), and
conversion into azirine 6g (63%) upon treatment with
experiment confirmed the necessity of water for the
transformation (Entry 11). Finally, we studied the role of the
solvent, and found that toluene, THF, and CH3CN were suitable,
albeit giving 3a in lower yields than 1,4-dioxane (Entries 12–14),
whereas DMSO and DMF were not suitable (Entries 15 and 16).
iodosobenzene. The structural diversity of these products, all of

3
which were accessed using inexpensive and readily available
reagents, underlines the potential of β-aminoacrylonitriles as
versatile synthetic intermediates.
kcal/mol, to produce an acetylinyl triphenylphosphine aza-ylide
intermediate I. This process determined the regiochemistry of
aminocyanation. Intermediate I can either undergo cyclization
(Fig. 2, path a), or N–N bond cleavage (Fig. 2, path b), with both
routes converging on intermediate IV. In path a, the 5-endo-dig
cyclization of activated intermediate I via TS2 generates a stable
five-membered pyrazole intermediate II through a low energy
barrier of 5.7 kcal/mol. From II, cleavage of the N–NC bond to
give intermediate IV is predicted to be the dominant pathway due
to the low free energy barrier of TS3 (3.6 kcal/mol); competing
hydrolysis of the phosphonium ion would instead give the
observed byproduct pyrazole 5b. In the alternative path b,
cleavage of the N–NC bond of intermediate I (via TS5, 6.4
kcal/mol) releases phenylproprionitrile 4b and silver
Scheme 2. Large scale synthesis and transformations of β-
aminoacrylonitrile 3b a
.
iminophosphorane III. The formation of intermediate IV from
III (through TS6) features a free energy barrier of 23.7 kcal/mol,
which is 20 kcal/mol higher in energy than that encountered with
TS3 in path a. These calculations, combined with the evidence
gathered from the experiments in Scheme 3 (Eq. 3), support path
b as an auxiliary pathway, and path a as the major
aminocyanation route; the high stereoselectivity of the reaction
may offer further support for the intermediacy of cyclic
intermediate IV. Finally, following protodemetalation of
intermediate IV to give V (via TS4), hydrolysis of the
a Reagents and conditions: (i) aniline hydrochloride, MeOH; (ii)
NaBH3CN, EtOH; (iii) HCl(aq.), CHCl3; (iv) NBS, CH2Cl2; (v)
K2S2O8, DMSO; (vi) phenylacetylene, (PhIO)n, BF3·OEt2, TFE; (vii)
(PhIO)n, CH2Cl2.
iminophosphorane affords aminoacrylonitrile 3b.18
Control experiments were carried out to probe the reaction
mechanism (Scheme 3). First, silver acetylide 7 and NIITP were
reacted under the optimized conditions, but in the absence of
Ag2CO3, which gave β-aminoacrylonitrile 3b in 56% yield (Eq.
1). This result supports a silver acetylide as a key reaction
intermediate. In contrast, the reaction of pyrazole 5b (an
observed byproduct of the reaction) under the optimized
conditions did not lead to the formation of any
β-aminoacrylonitrile product, suggesting that 5b is not an
intermediate en route to 3b (Eq. 2). Similarly, the attempted
reaction of 3-phenylproprionitrile 4b with triphenylphosphine
imide 8 afforded only trace amounts of product 3b, along with
the recovery of unreacted 4b (Eq. 3). This reveals that 4b and 8
can serve as intermediates for this reaction; albeit the efficiency
of their coupling is inferior to the reaction of 7 and 2.
Scheme 3. Mechanistic investigation.
Figure 2. Plausible reaction pathways
In summary, we have developed the first intermolecular
aminocyanation of alkynes, which utilizes NIITP – a readily
available functionalized isocyanide – as both the amine and
cyano source. This methodology enables the formation of β-
aminoacrylonitriles with excellent regio- and stereoselectivity;
these are shown to be valuable synthetic intermediates through
their transformation into a range of useful nitrile-containing
derivatives. Experimental and DFT studies support a reaction
pathway that proceeds through sequential isocyanide
Density functional theory (DFT) calculations (B3LYP)17 were
carried out to explore potential pathways consistent with these
experimental observations.18 This began with the C–H bond
activation of phenylacetylene by the silver ion released from
Ag2CO3. The calculated free energy barrier of this step is 8.6
kcal/mol, supporting the notion that the formation of silver
acetylide intermediate 7 is kinetically feasible.19 As shown in
Figure 2, following complexation of isonitrile 2, migratory
insertion of the silver acetylide to the terminal carbon atom of
isonitrile 2 then proceeds via TS1, with an energy barrier of 12.5
addition/cyclization, and N–N bond cleavage. This work
provides a new platform for the difunctionalization of C−C

4
Tetrahedron
Xu, Org. Lett, 2012, 14, 4614; Imines: (b) R. C. Cioc, H. D.
Preschel, G. van der Heijden, E. Ruijter, R. V. A. Orru, Chem. Eur.
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Alkyl halogens: (d) X. Jiang, J.-M. Wang, Y. Zhang, Z. Chen, Y.-
M. Zhu, S.-J. Ji, Tetrahedron 2015, 71, 4883.
multiple bonds; further applications of NIITP to this end are
ongoing in our laboratory.
Acknowledgments
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Financial support was provided by NSFC (21604082) and
the Department of Science and Technology of Jilin Province
(20190103128JH).
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Supplementary Material
Experimental details, analytical data for products, NMR
spectra of products, and X-ray data for 3o. Supplementary data to
this article can be found online at https://doi.org/xxxxxxxx.
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Click here to remove instruction text...
10. For examples of the cyanation of other substrates using
isocyanides, see: Heteroarenes: (a) S. Xu, X. Huang, X. Hong, B.

5
Highlights
(1) The first intermolecular aminocyanation of
alkynes.
(2) NIITP acts as both amine source and CN source.
(3) The highly regio- and stereoselective
aminocyanation.