Nickel-catalyzed aminocarbonylation of Aryl/Alkenyl/Allyl (pseudo)halides with isocyanides and H2O

Article abstract of DOI:10.1016/j.tetlet.2020.152605

Herein described is a nickel-catalyzed aminocarbonylation of aryl/alkenyl/allyl (pseudo)halides with isocyanides, providing aryl/alkenyl/allyl amides in 41% to 92% yields. Functional groups such as F, Cl, OMe, and heteroaromatic rings are compatible in the reaction. A Ni(0)/Ni(II) catalytic cycle is proposed based on preliminary experiments and previous literature. The reaction features readily available nickel salt, broad functional group tolerance, and simple reaction conditions.

Full text of DOI:10.1016/j.tetlet.2020.152605

Journal Pre-proofs
Nickel-Catalyzed Aminocarbonylation of Aryl/Alkenyl/Allyl (pseudo)halides
with Isocyanides and H O
2
Qiao Li, Cai Yun, Hongwei Jin, Yunkui Liu, Bingwei Zhou
PII:
S0040-4039(20)31104-7
DOI:
Reference:
https://doi.org/10.1016/j.tetlet.2020.152605
TETL 152605
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
8 September 2020
21 October 2020
23 October 2020
Please cite this article as: Li, Q., Yun, C., Jin, H., Liu, Y., Zhou, B., Nickel-Catalyzed Aminocarbonylation of
Aryl/Alkenyl/Allyl (pseudo)halides with Isocyanides and H O, Tetrahedron Letters (2020), doi: https://doi.org/
2
1
0.1016/j.tetlet.2020.152605
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover
page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version
will undergo additional copyediting, typesetting and review before it is published in its final form, but we are
providing this version to give early visibility of the article. Please note that, during the production process, errors
may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
©
2020 Published by Elsevier Ltd.

Nickel-Catalyzed Aminocarbonylation of Aryl/Alkenyl/Allyl (pseudo)halides with Isocyanides and H O
2
a
a
a
a
a
Qiao Li,† Cai Yun,† Hongwei Jin, Yunkui Liu,* and Bingwei Zhou*
aCollege of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
These authors contributed equally to this work
Abstract:
Herein described is a nickel-catalyzed aminocarbonylation of aryl/alkenyl/allyl (pseudo)halides with isocyanides,
†
providing aryl/alkenyl/allyl amides in 41% to 92% yields. Functional groups such as F, Cl, OMe, and heteroaromatic
rings are compatible in the reaction. A Ni(0)/(II) catalytic cycle is proposed based on preliminary experiments and
previous literature. The reaction features readily available nickel catalysis, broad functional group tolerance, and
simple reaction conditions.
The amide is ubiquitous in nature and plays unique role particularly in proteins, agrochemicals,
1
-2
pharmaceuticals, and polymers. Amides also serve as versatile building blocks to access a variety of useful
organic compounds through traditional transformations or transition metal-catalyzed C-C or C-N bond
3
activation. In this regard, the development of useful methods for amide preparation is highly desirable.
Although the condensation of carboxylic acid derivatives with amines is routinely employed as the most
robust process, transition metal-catalyzed aminocarbonylation of aryl/alkyl (pseudo)halides, CO, and
4
amines has been extensively investigated over the past several decades. In addition, the reductive
5
coupling reaction of isocyanates also provides a direct pathway for the amide synthesis. Notably,
isocyanide, as a serviceable C1 synthon is susceptible to the multicomponent reactions or one-pot cascade
6
reactions with nucleophiles, electrophiles, and radicals. Thus, one promising way to construct amide bond
can be achieved through the transition metal-catalyzed aminocarbonylation of aryl/alkyl (pseudo)halides,
7
isocyanides, and H O. It should be mentioned that precious metals such as palladium hold a dominant
2
8
9
position for the synthesis of aromatic/allyl amides while those reactions catalyzed by base metals are far
less developed.
Nickel salt has gained intense attention due to its rich abundance in earth crust and unique catalytic
reactivity of single electron transfer (SET) process which may not be readily accessible with palladium
analogs.10-11 The application of nickel catalysis to the amide synthesis using isocyanide as a carbonyl source
1
2
12a
has been reported more recently. For example, Qu and Chen group disclosed a nickel-catalyzed
aminocarbonylation of alkyl halides, isocyanides, and H O (Scheme 1a). This reaction characterizes a broad
2
o
substrate scope and excellent yields at 100 C. However, an air-sensitive Ni(COD) was employed as a
2
catalyst and alkyl iodines were used as electrophile in most cases. Soon later, Qu and Chen group12b again
described a nickel-catalyzed aminocarbonylation of secondary benzyl chlorides with isocyanides in which
halides (-I, -Br, -Cl) and heteroaromatic rings such as pyridine and pyrazine were fairly compatible (Scheme
1
b). Despite that alkyl halides have been successfully employed as vital electrophiles, the aryl and allyl

halides proceeding an aminocarbonylation under nickel catalysis to access the corresponding amides are
still underdeveloped. We herein present a nickel-catalyzed aminocarboxylation of aryl/alkenyl/allyl
(
pseudo)halides with isocyanides and H O (Scheme 1c). Utilizing NiBr as a catalyst and NHC as a ligand,
2
2
aryl, alkenyl, and allyl amides could be easily obtained in moderate to excellent yields, which provide a
novel strategy to construct the amide bond.
a) Ni-catalysed aminocarbonylation of alkyl halides with isocyanides
O
Alkyl
X
+
RNC
+
H2O
Ni
Alkyl
NHR
(
X = I, Br, Cl)
b) Ni-catalysed aminocarbonylation of secondary benzyl chlorides with
isocyanides
R1
O
R1
2
2
H O
Cl
+
R NC
+
Ni
NHR2
Ar
Ar
c) Ni-catalysed aminocarbonylation of aryl/alkenyl/allyl (pseudo)halides
with isocyanides (This work)
O
X
Ar
X = I, Br, Cl, OTf)
R1
+
RNC
+
H2O
Ni
Ni
NHR
Ar
(
O
X
R1
+
RNC
+
2
H O
NHR
R2
X = Br, Cl)
R2
(
alkenyl-/allyl- amides
Scheme 1. Nickel-catalyzed aminocarbonylation using isocyanide as a C1 source
At the beginning, we commenced the model reaction of 2-bromonaphthalene 1l, tert-butyl isocyanide
t
2
a, and H O under the conditions of Ni(dme)Cl (10 mol%), L1 (20 mol%), NaO Bu (2 equiv), and toluene (1
2
2
o
ml) at 150 C for 20 h. To our delight, the desired product 3l was isolated in 32% yield (Entry 1, Table 1).
Other nickel salts were then examined and it was found that NiBr was the most efficient catalyst (Entries
2
2
-5, Table 1). Control experiments indicated that nickel salt and ligand were critical to the catalytic cycle
(
Entries 6-7, Table 1). Next, tuning the volume ratio of H O to toluene further improved the yield to 90%
2
(Entries 8-12, Table 1, see Supporting Information for details). Ligand screening revealed that L1 remained
the best one compared with other NHC salts (Entries 13-17, Table 1). Neither phosphine nor nitrogen
ligands could promote the reaction (see Supporting Information for details). Different kinds of base were
t
investigated and the yields were inferior to that of NaO Bu (Entries 18-21, Table 1). Finally, either halving
the amount of nickel salt or lowing the reaction temperature resulted in a sharp decrease in yield (Entries
2
2-23, Table 1).
Table 1. Reaction parameter screening
O
Br
Catalyst, Ligand, Base
H2O, Solvent, Temp.
tBu
tBuNC
+
N
H
1l
2a
3l

nBu
nAmyl
Ph
Ph
N
N
N
N
N
N
N
N
N
N
Mes
Mes
Mes Mes
Mes
Mes
Mes
Mes
Mes
Mes
N
N
Mes
Mes
Cl
Cl
Cl
Cl
Cl
Cl
L1
L2
L3
L4
L5
L6
Entry
Catalyst (mol%)
Ligand
L1
L1
L1
L1
L1
-b
Base
H O : toluene (v/v, ml ) Temp./oC Yield/%
2
t
1
2
3
4
5
6
7
8
9
Ni(dme)Cl (10)
NaO Bu
0.1 ml: 1.0 ml
0.1 ml: 1.0 ml
0.1 ml: 1.0 ml
0.1 ml: 1.0 ml
0.1 ml: 1.0 ml
0.1 ml: 1.0 ml
0.1 ml: 1.0 ml
0.3 ml: 1.0 ml
0.5 ml: 1.0 ml
0.3 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
0.1 ml: 0.3 ml
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
130
32
64
57
30
72
0
2
t
Ni(acac) (10)
NaO Bu
2
t
Ni(cod) (10)
NaO Bu
2
t
NiCl (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
-c
L1
L1
L1
L1
L1
L2
L3
L4
L5
L6
L1
L1
L1
L1
L1
L1
NaO Bu
t
0
t
NiBr (10)
NaO Bu
76
65
80
90
43
65
0
2
t
NiBr (10)
NaO Bu
2
t
1
1
1
1
1
1
1
1
1
2
2
2
2
1
2
3
4
5
6
7
8
9
0
1
2
3
NiBr (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
t
NiBr (10)
NaO Bu
37
40
32
76
31
45
60
67
2
t
NiBr (10)
NaO Bu
2
t
NiBr (10)
LiO Bu
2
t
NiBr (10)
KO Bu
2
NiBr (10)
Na CO
2
2
3
NiBr (10)
NaOH
2
t
NiBr (5)
NaO Bu
2
t
NiBr (10)
NaO Bu
2
a
Reaction conditions: 1l (0.2 mmol), 2a (0.2 mmol), catalyst, ligand (20 mol%), base (2 equiv), H O, toluene,
2
b
c
at an indicated temperature for 20 h. No ligand. No catalyst.
With the optimized conditions in hand, we started to evaluate the substrate scope of aryl halides
(Scheme 2). Phenyl halides were first examined and bromobenzene exhibited a superior reactivity over
chloro/iodo analogs (3a, Scheme 2). A series of bromobenzenes with electron varied functional groups at

para-position were then screened (3b-h, Scheme 2). In general, the reaction was in favour of the substrates
bearing the electron donating group at phenyl ring. Note that the reaction of 1-bromo-4-chlorobenzene
gave a single product 3g albeit in a low yield, which suggested a good chemo-selectivity. Relatively lower
yields of 3i (vs 3b, 3j) and 3k (vs 3l) implied a steric hindrance effect on product outcome. It should be
mentioned that heteroaromatic bromides bearing pyridinyl, furyl, and thienyl were compatible with the
reaction conditions (3n-p, Scheme 2). In addition of aryl halides, alkenyl bromide was employed as an
electrophile as well. Both (E)-(2-bromovinyl)benzene and 1-bromo-2-methylprop-1-ene gave the desired
products in 86% and 81% yield, respectively (3q-r, Scheme 2). Aryl triflates instead of aryl halides exhibited
a comparable reactivity (3a, 3c, 3e-g, 3i, Scheme 2). We next examined the scope of isocyanide. Expectedly,
1
-adamantane isocyanide reacted with 1-bromonaphthalene and H O generating the corresponding
2
product in 67% yield (3s, Scheme 2). However, aryl and butyl isocyanides failed to deliver the amides even
for the prolonged reaction time.
NiBr2 (10 mol%)
L1 (20 mol%)
O
Br
t
NaO Bu (2 equiv)
R
+
RNC
Ar
N
H
H2O, toluene
Ar
o
1
50 C, 20 h
1
2
3
O
O
O
tBu
tBu
N
tBu
N
N
H
H
H
R
3
a: R = H, 78%, 34%b
3
i: 68%, 66%d
3j: 70%
5% , 73%d
c
6
3
3
3
3
3
3
3
b: R = Me, 75%
H
c: R = OMe, 87%, 88%d
O
N
O
tBu
tBu
d: R = NMe , 60%
2
N
e: R = Ph, 64%, 70%d
f: R = F, 60%, 64%d
g: R = Cl, 43%, 40%d
H
3
k: 50%
3l: 90%
h: R = CF , 53%
3
O
O
tBu
X
O
tBu
O
N
H
N
HN tBu
H
N
O
3
3
n: X = O, 92%;
o: X = S, 41%
3m: 82%
3p: 75%
O
O
O
tBu
tBu
Ad
N
Ph
N
N
H
H
H
3q: 86%
3r: 81%
3s: 67%
a
Scheme 2. Substrate scope of aryl/alkenyl (pseudo)halides. Reaction conditions: 1 (0.2 mmol), 2 (0.2
t
o
mmol), NiBr (10 mol%), L1 (20 mol%), NaO Bu (2 equiv), H O (0.1 ml), toluene (0.3 ml), at 150 C for 20 h.
2
2
b
c
d
From aryl chloride. From aryl iodine. From aryl triflate.
To our surprise, allyl bromide was also viable substrate providing an isomerized alkenyl amide 3t as major
product in 60% yield under the standard reaction conditions. The yield of 3t was further improved to 68%
if the reaction was conducted under the Conditions A. Notably, allyl chloride could give a comparable yield
(71%) with higher regio-selectivity (3t, Scheme 3). In contrast, other selected allyl halides reacting with 2a

provided allyl amides as major products with moderate to good regio-selectivities (4u-y, Scheme 3).
R1
X
O
O
R2
Conditions A
1
R1
tBu
R1
tBu
+
+
N
N
H
t
H
BuNC
R2
R2
2a
3
4
O
O
O
tBu
tBu
Ph
tBu
N
N
H
N
H
H
4u: 63%b (1:2)
4v: 43%b (1:7)
3
t: 68%b (13:1)
c
71% (23:1)
O
O
O
tBu
tBu
tBu
N
N
H
N
H
H
w: 61%b, d
4x: 70% (1:12)
c
4y: 68%c, e (1:14)
4
a
Scheme 3. Substrate scope of allyl halides. Conditions A: 1 (0.2 mmol), 2a (0.2 mmol), Ni(dppp)Cl (10
2
o
mol%), base (2 equiv), H O (0.3 ml), MeCN (0.5 ml), at 150 C for 12 h. The ratio of 3 to 4 was determined
2
1
b
by crude H NMR analysis and given in the parenthesis and major isomer was shown in Scheme 3. X = Br.
c
d
e
1
X = Cl. Single isomer. The Z/E ratio of 4y could not be determined by the crude H NMR analysis.
A gram-scale reaction of (E)-(2-bromovinyl)benzene 1q with tert-butyl isocyanide 2a was performed
under the standard reaction conditions (Scheme 4). Delightedly, the product 3q was isolated in a
synthetically useful yield. This result indicated that the nickel-catalyzed aminocarbonylation reaction might
be practically useful for the amide synthesis.
NiBr2 (10 mol%)
L1 (20 mol%)
t
O
NaO Bu (2 equiv)
Br
q: 10 mmol
tBuNC
tBu
+
Ph
H2O, toluene
Ph
N
H
o
150 C, 20 h
1
2a
3q: 75% (1.5 g)
Scheme 4. Gram-scale reaction
To clarify the possible reaction mechanism, we first conducted the radical trapping experiment (Scheme
). TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) and BHT (butylated hydroxytolueneand) were
5
respectively chosen as radical scavenger and subjected to the model reaction. As a result, these reactions
proceeded smoothly providing the product in good yields (Scheme 5a). It could be inferred that a radical
process might not be involved in the catalytic cycle. Next, stoichiometric experiments were carried out.
o
The model substrate 1l was treated with stoichiometric nickel salt, ligand, and base in toluene at 150 C for
3
h (Scheme 5b, eq. 1). Unfortunately, naphthalene could not be detected and the starting material 1l was
recovered. Then we conducted the similar reaction under the Conditions B with extra addition of tert-butyl
isocyanide 2a. The product 3l and 2-naphthonitrile 5 were isolated in 18% and 61% yield, respectively
(Scheme 5b, eq. 2). These results indicated that Ni-2 might be the key intermediate in the
aminocarbonylation reaction.

a) Radical trapping experiments
Br
O
Standard conditions
radical scavenger
tBu
tBuNC
+
N
H
1l
3l
radical scavenger
yield of 3l
TEMPO (1 equiv)
BHT (1 equiv)
75%
83%
b) Stoichiometric experiments
Br
Conditions B
2
H O
H
NiLn
1
l
l
(eq. 1)
(eq. 2)

Not detected
Ni-1
t
N Bu
Conditions B
tBuNC
2
H O
CN
1
3l +
NiLn
Br
(1 equiv)
Ni-2
18%
5: 61%
Conditions B: NiBr2 (1 equiv), L1 (1 equiv), NaO Bu (1 equiv), toluene, 150 oC, 3 h.
t
Scheme 5. Mechanistic experiments
1
3
Based on the mechanistic experiments and previous literature, we proposed a possible reaction
mechanism shown in Scheme 6. The catalytic reaction might be initiated by an in situ formed Ni(0) species
which coordinated with isocyanide to form Ni-3. An oxidative addition reaction of Ni-3 with aryl halide
resulted in the formation of aryl nickel species Ni-4, followed by a 1,1-migratory insertion into C-Ni bond
generating imidoyl nickel species Ni-2. The resulting Ni-2 reacted with H O in the presence of base giving
2
the intermediate Ni-5. Finally, a reductive elimination reaction took place to regenerate Ni-3 and release
the intermediate 3’ which fast tautermerized to stable aryl amide 3.
LnNi(0)
3
RNC
2
R
N
Ni(0)Ln
Ar X
NR
OH
Ni-3
1
Ar
3'
RNC
NR
Ni(II)Ln
2
Ar
Ar
R
N
Ni(II)Ln
X
OH
Ni-5
Ni-4
NR
H2O
+
Ar
Ni(II)Ln
t
NaO Bu
X
Ni-2
Scheme 6. Plausible reaction mechanism
In conclusion, we have developed a nickel-catalyzed aminocarboxylation reaction for the synthesis of
aryl/alkenyl/allyl amides. Aryl/alkenyl/allyl halides and aryl triflates are all competent to furnish this
reaction affording the amides in moderate to excellent yields. A variety of functional groups as well as
heteroaromatic rings such as pyridinyl, furyl, and thienyl were tolerated under the optimized conditions.
The further exploration of nickel-catalyzed aminocarbonylation involving isocyanide insertion is still

ongoing in our laboratory.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.
Acknowledgements
We thank the Natural Science Foundation of China (No. 21772176 and 21372201) and the Natural
Science Foundation of Zhejiang Province (LQ20B020012) for financial support.
Appendix A. Supplementary data
Supplementary material containing experimental procedures, characterization data and scanned copies of the
NMR spectra of all new compounds is provided.
Rreferences
1
2
3
(a) The Amide Linkage: Structural Significance in Chemistry, Bio-chemistry and Materials Science (Eds.: A.
Greenberg, C. M. Breneman, J. F. Liebman), Wiley-Interscience, New York, 2000; (b) V. R. Pattabiraman, J.
W. Bode. Nature 480(2011) 471; (c) R. M. Lanigan, T. D. Sheppard. Eur. J. Org. Chem. (2013) 7453; (d) H.
Lundberg, F. Tinnis, N. Selander, H. Adolfsson. Chem. Soc. Rev. 43(2014) 2714; (e) R. M. de Figueiredo, J.-
S. Suppo, J.-M. Campagne. Chem. Rev. 116(2016) 12029.
(a) S. D. Roughley, A. M. Jordan. J. Med. Chem. 54(2011) 3451; (b) J. R. Dunetz, J. Magano, G. A.
Weisenburger. Org. Process Res. Dev. 20(2016) 140; (c) T. Ai, R. Willett, J. Williams, R. Ding, D. J. Wilson, J.
Xie, D.-H. Kim, R. Puertollano, L. N. Chen. ACS Med. Chem. Lett. 8(2017) 90; (d) A. Buchynskyy, J. R. Gillespie,
M. A. Hulverson, J. McQueen, S. A. Creason, R. M. Ranade, N. A. Duster, M. H. Gelb, F. S. Buckner. Bioorg.
Med. Chem. 25(2017) 1571.
(a) M. Tobisu, K. Nakamura and N. Chatani. J. Am. Chem. Soc. 136(2014) 5587; (b) L. Hie, N. F. F. Nathel, T.
K. Shah, E. L. Baker, X. Hong, Y.-F. Yang, P. Liu, K. N. Houk, N. K. Garg. Nature 524(2015), 79; (c) S. Shi, G.
Meng, M. Szostak. Angew. Chem. Int. Ed. 55(2016) 6959; (d) J. Hu, Y. Zhao, J. Liu, Y. Zhang, Z. Shi. Angew.
Chem. Int. Ed. 55(2016) 8718; (e) T. B. Boit, N. A. Weires, J. Kim, N. K. Garg. ACS Catal. 8(2018) 1003; (f) M.
M. Mehta, T. B. Boit, J. E. Dander, N. K. Garg. Org. Lett. 22(2020) 1; (g) R. R. Knapp, A. S. Bulger, N. K. Garg.
Org. Lett. 22(2020) 2833.
4
(a) A. Brennführer, H. Neumann, M. Beller. Angew. Chem. Int. Ed. 48(2009) 4114; (b) X.-F. Wu, X. Fang, L.
Wu, R. Jackstell, H. Neumann, M. Beller. Acc. Chem. Res. 47(2014) 1041; (c) Y. Li, Y. Hu, X.-F. Wu. Chem.
Soc. Rev. 47(2018) 172; (d) J.-B. Peng, F.-P. Wu, X.-F. Wu. Chem. Rev. 119(2019), 2090.

5
6
(a) E. Serrano, R. Martin. Eur. J. Org. Chem. (2018) 3051; (b) T. Michiyuki, I. Osaka, K. Komeyama. Chem.
Commun. 56(2020) 1247.
(a) A. Dömling, I. Ugi. Angew. Chem. Int. Ed. 39(2000) 3168; (b) J. Zhu. Eur. J. Org. Chem. (2003) 1133; (c)
A. Dömling. Chem. Rev. 106(2006) 17; (d) S. Chakrabarty, S. Choudhary, A. Doshi, F.-Q. Liu, R. Mohan, M.
P. Ravindra, D. Shah, X. Yang, F. F. Fleming. Adv. Synth. Catal. 356(2014) 2135.
7
(a) S. Lang. Chem. Soc. Rev. 42(2013) 4867; (b) T. Vlaar, E. Ruijter, B. U. W. Maes, R. V. A. Orru. Angew.
Chem. Int. Ed. 52(2013) 7084; (c) G. Qiu, Q. Ding, J. Wu. Chem. Soc. Rev. 42(2013) 5257; (d) V. P. Boyarskiy,
N. A. Bokach, K. V. Luzyanin, V. Y. Kukushkin. Chem. Rev. 115(2015) 2698; (e) B. Zhang, A. Studer. Chem.
Soc. Rev. 44(2015) 3505; (f) B. Song, B. Xu. Chem. Soc. Rev. 46(2017) 1103; (g) J. W. Collet, T. R. Roose, E.
Ruijter, B. U. W. Maes, R. V. A. Orru. Angew. Chem. Int. Ed. 59(2020) 540.
8
9
For selected examples, see: (a) H. Jiang, B. Liu, Y. Li, A. Wang, H. Huang. Org. Lett. 13(2011) 1028; (b) G.
Qiu, M. Mamboury, Q. Wang, J. Zhu. Angew. Chem. Int. Ed. 55(2016) 15377.
Sparse examples of Cu-catalyzed aminocarbonylation, see: (a) I. Yavari, M. Ghazanfarpour-Darjani, M. J.
Bayat. Tetrahedron Lett. 55(2014) 4981; (b) Y. Li, J. Cao, Q. Zhu, X. Zhang, G. Shi, J. Russ. Gen. Chem.
8
6(2016) 668.
1
1
0 (a) J. Breitenfeld, J. RuizSoc, M. D. Wodrich, X. Hu. J. Am. Chem. Soc. 135(2013) 12004; (b) S. Z. Tasker, E.
A. Standley, T. F. Jamison. Nature 509(2014) 299; (c) V. P. Ananikov. ACS Catal. 5(2015) 1964; (d) M. M.
Beromi, A. Nova, D. Balcells, A. M. Brasacchio, G. W. Brudvig, L. M. Guard, N. Hazari, D. J. Vinyard. J. Am.
Chem. Soc. 139(2017) 922; (e) H. Yin, G. C. Fu. J. Am. Chem. Soc. 141(2019) 15433.
1 (a) D. J. Weix. Acc. Chem. Res. 48(2015) 1767; (b) X. Wang, Y. Dai, H. Gong. Top Curr. Chem. 374(2016), 43;
(c) T. Iwasaki, N. Kambe. Top Curr. Chem. 374(2016) 66; (d) M. Börjesson, T. Moragas, D. Gallego, R. Martin.
ACS Catal. 6(2016) 6739; (e) J. Choi, G. C. Fu. Science 356(2017) eaaf7230; (f) A. Tortajada, F. Juliá-
Hernández, M. Börjesson, T. Moragas, R. Martin. Angew. Chem. Int. Ed. 57(2018) 15948; (g) R. Shi, Z. Zhang,
X. Hu. Acc. Chem. Res. 52(2019) 1471.
1
1
2 (a) W. Huang, Y. Wang, Y. Weng, M. Shrestha, J. Qu, Y. Chen. Org. Lett. 22(2020) 3245; (b) Y. Wang, W.
Huang, C. Wang, J. Qu, Y. Chen. Org. Lett. 22(2020) 4245.
3 (a) K. Matsubara, K. Ueno, Y. Koga, K. Hara. J. Org. Chem. 72(2007) 5069; (b) P. Leowanawat, N. Zhang, M.
Safi, D. J. Hoffman, M. C. Fryberger, A. George, V. J. Percec. Org. Chem. 77(2012) 2885; (c) E. A. Standley,
T. F. Jamison. J. Am. Chem. Soc. 135(2013) 1585.

Graphical abstract
O
X
Ar
X = I, Br, Cl, OTf)
R1
+
RNC + H2O
Ni
Ni
NHR
Ar
(
O
X
R1
+
RNC + H O
2
NHR
R2
X = Br, Cl)
R2
(
alkenyl-/allyl- amides
25 examples, yield up to 92%
Highlights:



A nickel-catalyzed aminocarbonylation is reported.
Aryl/alkenyl/allyl (pseudo)halides are viable substrates.
A Ni(0)/Ni(II) catalytic cycle is proposed.
S1