Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst

Article abstract of DOI:10.1055/s-0040-1705943

A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.

Full text of DOI:10.1055/s-0040-1705943

SYNLETT
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart
2020, 31, A–E
cluster
A
Modern Nickel-Catalyzed Reactions
K. Iizumi et al.
Cluster
Synlett
Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters
and Organocyanides by a Nickel Catalyst
Keiichiro Iizumia
Ni-catalyzed decarbonylative cyanation of aromatic esters
Miki B. Kurosawaa
Ryota Isshikia
Kei Mutob
Junichiro Yamaguchi*a
S
O
CN
P
P
CN
+
OPh
N
Ni
0
0
0
0
-
0
0
0
2
-
3
8
9
6
-
5
8
8
2
R
R
a Department of Applied Chemistry, Waseda University, 513
Wasedatsurumakicho, Shinjuku, Tokyo, 162-0041, Japan
junyamaguchi@waseda.jp
b Institute for Advanced Study, Waseda University,
513 Wasedatsurumakicho, Shinjuku, Tokyo, 162-0041,
Japan
♦ Halogen-free ♦ Nonmetal cyanating reagent ♦ Inexpensive metal catalyst
Published as part of the Cluster Modern Nickel-Catalyzed Reactions
Corresponding Author
Junichiro Yamaguchi
Received: 24.08.2020
Accepted after revision: 17.09.2020
Published online: 16.10.2020
nides and non-halogen-based aryl electrophiles remain ra-
re; our previous Ni-catalyzed cyanation of arenols with
aminoacetonitriles10 is one such example (Figure 1b).11,12
Meanwhile, our group and others have extensively stud-
ied the development of metal-catalyzed decarbonylative
cross-coupling of aromatic esters, because these com-
pounds are abundant and easily prepared.13–15 Our group
discovered that the use of the thiophene-based diphos-
DOI: 10.1055/s-0040-1705943; Art ID: st-2020-k0464-c
Abstract A decarbonylative cyanation of aromatic esters with amino-
acetonitriles in the presence of a nickel catalyst was developed. The key
to this reaction was the use of a thiophene-based diphosphine ligand,
dcypt, permitting the synthesis of aryl nitrile without the generation of
stoichiometric metal- or halogen-containing chemical wastes. A wide
range of aromatic esters, including hetarenes and pharmaceutical mol-
ecules, can be converted into aryl nitriles.
phine
3,4-thiene-2,3-diylbis(dicyclohexylphosphine)
(dcypt)16 as an ancillary ligand for nickel and palladium cat-
alysts showed a good performance in various decarbonyla-
tive coupling reactions of aromatic esters with nucleo-
philes. We then sought to extend the scope of these decarbo-
nylative reactions to cyanation. Although it is known that
aromatic esters can be transformed into aryl nitriles
through a stepwise procedure involving hydrolysis, primary
Key words nickel catalysis, cyanation, aromatic esters, aminoacetoni-
triles, coupling reaction
Aryl nitriles are important structures in pharmaceuti-
cals and organic electronic materials.1 A method widely
used for synthesizing these molecules is the metal-cata-
lyzed cyanation of haloarenes with cyanating reagents (Fig-
ure 1a).2 Recently, this area of chemical methodology has
evolved to make the process of synthesizing aryl nitriles
cleaner and safer. Conventionally, metal cyanides such as
CuCN,3 Zn(CN)2,4 KCN,5 TMSCN,6 or others7 are often used.
Although these reagents are reliable, the generation of haz-
ardous HCN and stoichiometric metal waste is often prob-
lematic. Replacing metal cyanides with organic cyano com-
pounds such as cyanohydrins or acetonitrile has permitted
a safe and practical synthesis of aryl nitriles.8 Another con-
sideration in this area is the use of aryl electrophiles other
than haloarenes to avoid the production of corrosive halo-
gen-containing wastes during the reactions. To this end, al-
ternative catalytic methods using arenol- or aniline-based
electrophiles have emerged.9 Despite this progress toward
streamlined cyanation protocols, methods that achieve the
replacement of both coupling partners with organic cya-
A. Ni- and Pd-catalyzed cyanation
Hal
CN
Ni or Pd catalyst
+
M–CN
Zn(CN)2, CuCN,
KCN, TMSCN, etc.
B. Our previous work: Ni-catalyzed cyanation of arenols
CN
OR
CN
Ni catalyst
+
N
R
R
R: Piv, CONMe2, aminoacetonitriles
Ts, Ms, etc.
C.This work: Ni-catalyzed decarbonylative cyanation of aromatic esters
O
CN
CN
Ni catalyst
OPh
+
N
R
R
aminoacetonitriles
♦ Halogen-free ♦ Nonmetal cyanating reagent ♦ Inexpensive metal catalyst
Figure 1 Metal-catalyzed cyanations
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
K. Iizumi et al.
Cluster
Synlett
amide formation, and dehydration, a decarbonylative cou-
pling would make the synthesis of aryl nitriles shorter and
more straightforward. Before this study, the Rueping group
reported a decarbonylative cyanation of aromatic esters by
using nickel catalysis, albeit with Zn(CN)2 as a cyano
source.17 Here, we report the development of a decarbon-
ylative cyanation of aromatic esters with aminoacetoni-
triles as nonmetal cyanating reagents (Figure 1c).
At the outset of this study, we explored the reaction
conditions by using phenyl 2-naphthoate (1A) and mor-
pholin-4-ylacetonitrile (2a) as model reactants (Table 1).
Pleasingly, our initial attempt using Ni(OAc)2 (5 mol%),
dcypt, and Na3PO4 in 1,4-dioxane at 150 °C gave 2-naphtho-
nitrile (3A) in 23% yield (Table 1, entry 1). Encouraged by
this result, we first surveyed the effect of various ligands.
Despite being a structurally similar ligand, ethane-1,2-diyl-
10 mol% Ni(OAc)2
20 mol% dcypt
CN
O
Na2CO3 (1.5 equiv)
Table 1 Condition Optimizationa
N
CN
+
Ar
OPh
Ar
1,4-dioxane
160 °C, 12 h
O
5.0 mol% Ni(OAc)2
10 mol% Ligand
Base (1.5 equiv)
CN
1
2a (2.0 equiv)
3
O
CN
N
+
OPh
Structure of 3
Solvent
150 °C, 12 h
CN
CN
CN
O
1A
2a (2.0 equiv)
3A
Me
3A: 63%
76%a,b
3B: 47%a
73%a,b
3C: 48%c
69%a,b
S
N
N
Cy
Cy
P
P
P
P
CN
CN
CN
CN
CN
dcypt
dcype
ICy
MeO
3D: 55%
3E: 59%
3F: 50%d
3I: 51%a
3L: 45%a
Entry
Ligand
Base
Solvent
Yieldb (%)
1
2
dcypt
dcype
dppe
Na3PO4
Na3PO4
Na3PO4
Na3PO4
Na3PO4
Na3PO4
K3PO4
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
1,4-dioxane
toluene
23
Me
CN
CN
7
Me
3G: 40%a
3H: 46%a
CN
3
0
4
PCy3·HBF4
PBu3
0
MeO
CN
5
0
MeO
OMe
6
ICy·HBF4
dcypt
dcypt
dcypt
dcypt
dcypt
dcypt
dcypt
dcypt
0
a
3K: 64%a
3J:
31%
79%a,b
7
15
8
Li3PO4
0
CN
Me2N
CN
CN
9
K2CO3
17
Me2N
OPh
10
11
12c,d
13c
14c
Na2CO3
none
44
3M: 26%d
3N: 68%a
3O: 62%a,b
CN
21
CN
CN
CN
nPr
nPr
Na2CO3
Na2CO3
Na2CO3
62 (57)e
63
Me
S
N
NC
MeO2C
S
O
O
O
O
3P: 68%d
3R: 53%d
3S: 55%d
t-AmylOH
47
3Q: 66%
from probenecid
Aminoacetonitrilesf
CN CN
OMe
CN
CN
CN
CN
CN
CN
CN
CN
CN
N
O
N
N
N
N
N
SPh
Me
Me
N
N
N
Me
Ph
3T: 43%a
3U: 58%d
3V: 51%c
2a: 54%
2b: 52%
2c: 38%
2d: 51%
2e: 19%
2f: 0%
2g: 0%
CN
CN
a Reaction conditions: 1A (0.20 mmol), 2a (0.40 mmol), Ni(OAc)2 (5.0
mol%), ligand (bidentate: 10 mol%; monodentate: 20 mol%), base (1.5
N
N
equiv), solvent (0.80 mL), 150 °C, 12 h.
3W: 44%a
3X: 19%a,d
3Y: 33%a
b GC yield.
(55%)e
c Ni(OAc)2 (10 mol%), dcypt (20 mol%).
d 160 °C.
Scheme 1 Substrate scope. Reagents and conditions: 1 (0.40 mmol), 2a
(0.80 mmol), Ni(OAc)2 (10 mol%), dcypt (20 mol%), Na2CO3 (1.5 equiv),
1,4-dioxane (1.6 mL), 160 °C, 12 h. a 24 h. b Toluene solvent instead of
1,4-dioxane. c Na3PO4 instead of Na2CO3. d 150 °C. e 1H NMR yield.
e Isolated yield.
f Reaction conditions: 1A (0.20 mmol), 2a–g (0.40 mmol), Ni(OAc)2 (10
mol%), dcypt (20 mol%), Na2CO3 (1.5 equiv), 1,4-dioxane (0.80 mL), 150 °C,
12 h.
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

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K. Iizumi et al.
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bis(dicyclohexylphosphine) (dcype) decreased the yield of
3A to 7% (entry 2). 1,2-Bis(diphenylphosphino)ethane
(dppe), a less electron-donating ligand, did not give 3A at all
(entry 3). Monodentate phosphines and N-heterocyclic car-
bene ligands were totally ineffective, resulting in no reac-
tion (entries 4–6). With dcypt, the effect of base was then
investigated. Changing from Na3PO4 to K3PO4 or Li3PO4 did
not improve the yield (entries 7 and 8). We found that car-
bonate bases were superior to phosphates; in particular, the
use of Na2CO3 gave the best result (entries 9 and 10). A reac-
tion without a base also furnished the product, albeit in
only 21% yield (entry 11). At this time, the precise role of
the base is unclear. Increasing the catalyst loading to 10
mol% and the temperature to 160 °C gave a better yield of
3A (62%; entry 12). We found that toluene was also an ef-
fective solvent, giving 3A in almost comparable yield (entry
13). tert-Amyl alcohol (t-AmylOH) also delivered 3A in 47%
yield, but this was accompanied by significant decomposi-
tion of 1A (entry 14). We also screened various organic cya-
nides and we found that morpholin-4-ylacetonitrile (2a)
was the best option. Piperidin-1-yl-, pyrrolidin-1-yl, 4-
methylpiperazin-1-yl, and (dimethylamino)acetonitriles
also gave 3A, albeit in lower yields. The use of aminonitriles
was important, because neither phenylacetonitrile nor
(phenylsulfanyl)acetonitrile gave any 3A. Finally, we identi-
fied the optimal conditions as involving the use of
Ni(OAc)2/dcypt catalyst and Na2CO3 in 1,4-dioxane or tolu-
ene at 160 °C.
With the optimized conditions in hand, we examined
the scope of this decarbonylative cyanation (Scheme 1). 1-
Naphthonitrile (3B) was generated in a lower yield (47%)
than 2-naphthonitrile (3A), even at higher temperatures;
this decrease was probably due to steric hindrance. Naph-
thalenes bearing electron-donating substituents were con-
verted into the corresponding aryl nitriles 3C and 3D in
moderate yields. Anthracene and pyrene derivatives also
showed good reactivities in this decarbonylative cyanation,
giving 3E and 3F, respectively. Various benzoic acid deriva-
tives were also readily cyanated: 4- and 3-methylbenzoni-
trile (3G and 3H, respectively) were obtained from the cor-
responding aromatic esters. Although the yield of 2-methyl-
benzonitrile was less than 5% (see Supporting Information),
phenyl 9H-fluorene-1-carboxylate (1I) gave nitrile 3I in a
moderate yield (51%). 2-, 3-, and 4-Methoxybenzonitriles
(3J, 3K, and 3L, respectively) were all generated in accept-
able yields. Nitriles containing other electron-donating sub-
stituents such as dimethylamino (3M, 3N) or phenoxy (3O)
groups were also readily obtained. Moreover, the present
protocol was compatible with various electron-deficient ar-
omatic esters, providing the corresponding aryl nitriles
bearing cyano (3P), methoxycarbonyl (3Q), and or sulfone
groups (3R) in moderate to good yields. A pharmaceutically
important aromatic ester derived from probenecid, con-
taining a sulfonamide group, readily reacted under the con-
ditions to give nitrile 3S in 55% yield. Furthermore, the
present conditions could be applied to heteroaromatic es-
ters, and various quinolinyl and pyridyl nitriles 3T–X were
obtained in moderate yields. Finally, we succeeded in syn-
thesizing cinnamonitrile (3Y), albeit in only 33% yield.18
To gain insights into the mechanism of this reaction, we
conducted several control experiments (Scheme 2). First,
we subjected various arylcarboxylic acid derivatives such as
the acid chloride 417b acid anhydrides 5 and 6, aldehyde 7,
and methyl ester 8 to the reaction conditions (Scheme 2A).
However, none of these gave the desired aryl nitrile 3A.
A
10 mol% Ni(OAc)2
20 mol% dcypt
Na2CO3 (1.5 equiv)
CN
O
CN
N
O
+
X
1,4-dioxane
150 °C, 12 h
1A, 4–8
2a (2.0 equiv)
3A
O
O
O
O
Cl
OPiv
O
2
4 (0%)
5 (0%)
6 (0%)
O
O
H
OMe
OPh
7 (0%)
8 (0%)
1A (62%)
B
C
10 mol% Ni(OAc)2
20 mol% dcypt
Na2CO3 (1.5 equiv)
O
CN
+
NaCN
OPh
1,4-dioxane
150 °C, 12 h
1A
3A: 26%
10 mol% Ni(OAc)2
20 mol% dcypt
Na2CO3 (1.5 equiv)
via
O
dcypt
NiII
CN
CN
Ar
CN
1,4-dioxane
150 °C, 12 h
9
3B: 71%
D
1A
10 mol% Ni(OAc)2
20 mol% dcypt
Na2CO3 (1.5 equiv)
+
CN
CN
+
N
O
OH
N
O
1,4-dioxane
160 °C, 12 h
2a
3A: 57%
10: 41%
E
CN
Ni(OAc)2
–
10 mol% 20 mol% 38
10 mol% 40
dcypt
–
10/%
0
Na2CO3
N
O
N
O
OH
+
1,4-dioxane
150 °C, 5 h
ONa
–
2a (2.0 equiv) 11 (1.0 equiv)
10
O
N
[Ni]
PhONa
CN
Scheme 2 (A) Reactions using other aryl sources. (B) A reaction with
NaCN. (C) A reaction of acyl nitrile 9 (D) (Aminoalkyl)phenol 10 as a by-
product with 3A. (E) Postulated mechanism for the release of cyanide
from 2a.
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

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K. Iizumi et al.
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Synlett
NaCN, a typical cyanating agent, was then used instead of
2a, giving 3A in 26% yield (Scheme 2B). Moreover, the use of
acyl nitrile 9 under the standard conditions gave a good
yield of 1-naphthonitrile (3B; Scheme 2C).17a These results
support the involvement of a cyanide (CN–) species under
the present catalytic conditions, generating an aryl–Ni–CN
species as a catalytic intermediate. During our investiga-
tions, we found that the reaction of nitrile 2a gave the (ami-
noalkyl)phenol 10 as a byproduct in 41% yield (Scheme 2D).
This result indicated that the aminoacetonitrile 2a releases
cyanide along with the generation of an iminium species.
To shed light on the mechanism of this cyanide-releasing
step, we conducted the reaction between 2a and sodium
phenoxide (11) in the presence of Na2CO3 (Scheme 2E). This
reaction did not proceed at all; however, the same reaction
with a nickel catalyst afforded 10 in 40% yield. Although the
detailed role of nickel is unclear at this stage, this result
shows that the nickel catalyst is involved in the cyanide-re-
leasing process.
Taking these control experiments into consideration, we
postulated the following Ni(0)/Ni(II) catalytic cycle (Scheme
3). The reaction might be initiated by oxidative addition of 1
to a Ni(0) species, followed by decarbonylation to give an
aryl–Ni(II)–OPh species. Cyanide transfer from the amino-
acetonitrile to the Ni(II) species could occur to give an aryl–
Ni(II)–CN species that might finally release product 3
through reductive elimination.
Funding Information
This work was supported by JSPS KAKENHI Grant Number
JP19H02726 (to J.Y.), JP20H04829 (hybrid catalysis), and JP19K15573
(to K.M.).JapanSocietyforth
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Acknowledgment
The Materials Characterization Central Laboratory in Waseda Univer-
sity is acknowledged for their support of the HRMS measurements.
Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1705943. Su
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p
ortingInformatio
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References and Notes
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O
S
CN
OPh
Ar
Ar
– CO
P
P
Ni0
3
1
reductive
elimination
oxidative addition;
decarbonylation
S
S
P
P
P
P
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NiII
NiII
CN
OPh
Ar
Ar
CN transfer
CN
N
O
N
+
O
Ph
N
O
OH
O
2a
Scheme 3 A plausible catalytic cycle
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presence of a Ni/dcypt catalyst.19 The method not only pro-
vided a direct synthesis of aryl nitriles from esters, but also
permits halogen- and metal-waste-free catalytic cyanation.
Further studies to shed light on the detailed mechanism of
this reaction and to develop a method with a broader scope
are underway in our laboratory.
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see: (b) Wang, Z.; Wang, X.; Ura, Y.; Nishihara, Y. Org. Lett. 2019,
21, 6779.
(18) A main reason for the modest yield of some products was the
decomposition of the phenyl esters to the corresponding car-
boxylic acids.
(9) (a) Gan, Y.; Wang, G.; Xie, X.; Liu, Y. J. Org. Chem. 2018, 83,
14036. (b) Xu, W.; Xu, Q.; Li, J. Org. Chem. Front. 2015, 2, 231.
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Chem. 2015, 6606.
(11) Takise, R.; Itami, K.; Yamaguchi, J. Org. Lett. 2016, 18, 4428.
(12) Wang, L.; Wang, Y.; Shen, J.; Chen, Q.; He, M.-Y. Org. Biomol.
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(13) (a) Takise, R.; Muto, K.; Yamaguchi, J. Chem. Soc. Rev. 2017, 46,
5864. (b) Shi, S.; Nolan, S. P.; Szostak, M. Acc. Chem. Res. 2018,
51, 2589. (c) Guo, L.; Rueping, M. Chem. Eur. J. 2018, 24, 7794.
(d) Lu H., Yu T.-Y., Xu P.-F., Wei H.; Chem. Rev.; 2020, in press;
DOI: 10.1021/acs.chemrev.0c00153
(14) For selected examples of decarbonylative C–C bond formations,
see: (a) Chatani, N.; Tatamidani, H.; Ie, Y.; Kakiuchi, F.; Murai, S.
J. Am. Chem. Soc. 2001, 123, 4849. (b) Gooßen, L. J.; Paetzold, J.
Angew. Chem, Int. Ed. 2002, 41, 1237. (c) Gooßen, L. J.; Paetzold,
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Yamaguchi, J.; Itami, K. J. Am. Chem. Soc. 2012, 134, 13573.
(e) Meng, L.; Kamada, Y.; Muto, K.; Yamaguchi, J.; Itami, K.
Angew. Chem. Int. Ed. 2013, 52, 10048. (f) Muto, K.; Yamaguchi,
J.; Musaev, D. G.; Itami, K. Nat. Commun. 2015, 6, 7508. (g) Okita,
T.; Kumazawa, K.; Takise, R.; Muto, K.; Itami, K.; Yamaguchi, J.
Chem. Lett. 2017, 46, 218. (h) Isshiki, R.; Takise, R.; Itami, K.;
Muto, K.; Yamaguchi, J. Synlett 2017, 28, 2599. (i) Liu, X.; Jia, J.;
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(19) 2-Naphthonitrile (3A); Typical Procedure
A 20-mL glass vessel, equipped with a J. Young O-ring tap and a
magnetic stirring bar, was charged with Ni(OAc)2·4 H2O (10.0
mg, 0.040 mmol, 10 mol%) and Na2CO3 (63.6 mg, 0.60 mmol, 1.5
equiv). The vessel was evacuated and its contents were dried
with a heat gun. The vessel was then cooled to r.t., and filled
with N2 gas. Phenyl 2-naphthoate (1A; 99.3 mg, 0.40 mmol, 1.0
equiv), 2-morpholinoacetonitrile (2a: 100.9 mg, 0.80 mmol, 2.0
equiv), and dcypt (38.1 mg, 0.080 mmol, 20 mol%) were added,
and the vessel was evacuated and refilled with N2 gas three
times. Toluene (1.6 mL) was added, and the vessel was sealed
with the O-ring tap and heated at 160 °C in a nine-well reaction
block for 24 h with stirring. The mixture was then cooled to r.t.
and passed through a short silica-gel pad with EtOAc as an
eluent. The filtrate was concentrated in vacuo, and the residue
was purified by preparative TLC (hexane–EtOAc, 4:1) to give a
white solid; yield: 46.3 mg (76%) (CAUTION! The reaction should
be conducted in a well-functioning fume hood to avoid expo-
sure to the CO gas generated by the reaction. After the reaction,
the vessel should be opened in the fume hood for the same rea-
son.)
1H NMR (400 MHz, CDCl3):  = 8.23 (s, 1 H), 7.93–7.87 (m, 3 H),
7.67–7.58 (m, 3 H). 13C NMR (101 MHz, CDCl3):  = 134.6, 134.1,
132.2, 129.1, 129.0, 128.4, 128.0, 127.6, 126.3, 119.2, 109.3.
HRMS (DART): m/z [M + NH4]+ calcd for C11H11N2: 171.0917;
found: 171.0915.
(15) For selected examples of decarbonylative carbon–heteroatom
bond formations, see: (a) Pu, X.; Hu, J.; Zhao, Y.; Shi, Z. ACS
Catal. 2016, 6, 6692. (b) Guo, L.; Chatupheeraphat, A.; Rueping,
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E