Practical heterogeneous photoredox/nickel dual catalysis for C-N and C-O coupling reactions

Article abstract of DOI:10.1039/c9cc00987f

Efficient C-N and C-O coupling reactions of aryl halides with amines and alcohols have been developed by using the strategy of heterogeneous visible light photoredox and nickel dual catalysis. Obviously, the joint use of inexpensive and bench-stable CdS and nickel salts, together with mild reaction conditions, makes these two transformations attractive for the synthetic community. This heterogeneous dual catalysis system also proved to be successful in the ligand-free catalytic hydroxylation of aryl bromide with water as a nucleophile. The practicality of this protocol is further emphasized by the scaled-up reaction and the reusability of heterogeneous photocatalysts.

Full text of DOI:10.1039/c9cc00987f

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Practical heterogeneous photoredox/nickel dual catalysis
for C-N and C-O coupling reactions†
3Received 00th April 20xx,
Accepted 00th May 20xx
Yi-Yin Liu,a Dong Liang,a Liang-Qiu Lu*a,b and Wen-Jing Xiaoa,c
DOI: 10.1039/x0xx00000x
www.rsc.org/
using the semiconductor CdS and a chiral secondary amine
catalyst.6 In 2017, Krauss, Weix and coworkers reported an
impressive work on utilizing CdSe quantum dots (QDs) as efficient
photocatalysts for carbon-carbon bond formzation along with a
single case for carbon-nitrogen coupling.7 Even though, the
application of dual catalysis8 using heterogeneous photocatalysts
for C-heteroatom bond formation has been much less explored.7,9,10
Efficient C-N and C-O coupling reactions of aryl halides with
amines and alcohols have been developed through the strategy of
heterogeneous visible light photoredox and nickel dual catalysis.
Obviously, the joint use of inexpensive and bench-stable CdS and
nickel salts, together with mild reaction conditions, makes these
two transformations attractive for the synthetic community. This
heterogeneous dual catalysis system also proved to be successful
in the ligand-free catalytic hydroxylation of aryl bromide with
water as a nucleophile. The practicality of this protocol is further
emphasized by the scaled-up reaction and the reusability of
heterogeneous photocatalysts.
a) Previous work: C-N/C-O couplings via dual homogeneous catalysis
X
Br
Ir
X= NH, O
b) Our previous work: alcohol oxidations via dual heterogeneous catalysis
Ni
R
HX
+
R
OH
O
CdS, NiCl2.6H2O
Visible light photoredox catalysis has attracted increasing
attention from the synthetic community due to its powerful
capacity in organic synthesis.1 Generally, a photosensitizer is
required for harvesting visible light energy and further promoting
subsequent organic reactions.2,3 Though great achievements have
been made in the field of homogeneous visible light photocatalysis,2
from the perspective of green and sustainable synthetic chemistry,4
the exploitation of heterogeneous variants might be more practical
and attractive for industry,3 because, compared with the widely
used Ir- or Ru-based photocatalysts, heterogeneous photocatalysts,
including semiconductors such as TiO2 and CdS, are usually much
cheaper, more readily available and reusable. While, fewer efforts
have been made for chemical bond formation in organic synthesis,
albeit considerably more effort has been devoted to water splitting
and hydrogen generation.5 In 2012, Kӧnig and coworkers developed
a heterogeneous enantioselective α-alkylation of aldehydes by
+
H2
R1 R2
R1, R2= alkyl, aryl, H
R1 R2
This work:
c)
C-N/C-O couplings via dual heterogeneous catalysis
aldehydes, ketones,
imines, acids...

Br
+
CdS
HX
R
NiCl2•6H2O
X
X= NH, O

R
Scheme 1 Coupling reactions via photoredox/nickel dual catalysis
Aromatic amines and ethers are important motifs prevalent in
plenty of natural products, pharmaceuticals, and agrochemicals.11
C-N and C-O coupling reactions of aryl halides with amines and
alcohols, including the Buchwald-Hartwig and Ullmann coupling
reactions through Pd and Cu catalysis, respectively, are among the
most useful approaches to access these compounds.13,14 In recent
years, photoredox/Ni dual catalysis15 has drawn increasing
attention in the field of C-N16 and C-O couplings17 because it utilizes
mild reaction conditions. Ir-based photocatalysts are indispensable
for these transformations (Scheme 1, a). Recently, Xu and our lab
cooperatively accomplished visible light-driven heterogeneous
dehydrogenative oxidation of alcohols to carbonyls by merging CdS
and Ni catalysis (Scheme 1, b).18 Due to continuous interest in
visible light photocatalysis19 and transition metal catalysis,20 we
wish to further exploit the feasibility of this heterogeneous catalysis
strategy for C-N and C-O coupling reactions of aryl halides with
amines and alcohols (Scheme 1, c), albeit accompanying with the
potential dehydrogenative oxidation of amines and alcohols.21-23
aCCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide &
Chemical Biology, Ministry of Education, College of Chemistry, Central
China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Email: luliangqiu@mail.ccnu.edu.cn
bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou
Institute of Chemical Physics (LICP), Chinese Academy of Sciences,
Lanzhou 730000, China
cState Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, CAS, Shanghai 200032, China
†Electronic supplementary information (ESI) available. See DOI:
10.1039/0000000000
This journal is © The Royal Society of Chemistry 20xx
Chem. Commun., 2016, 00, 1-3 | 1
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We initially tested the heterogeneous C-N coupling reaction
with 4-bromobenzotrifluoride and pyrrolidine. A quick investigation
of Ni salts, ligands, solvents and light sources revealed that the
combination of CdS, NiCl2•6H2O and DMA could provide the aniline
product 3aa in 83% yield under irradiation with 6 W blue LEDs, with
no detection of oxidized by-products from pyrrolidine (entry 1).
3aa
3ba
3ca
3da
3ea
, R = CF3:
, R = CN:
, R = Ac:
, R = NO2: 62%
, R = CO2Et: 98%
, R = SO2Me: 96%
83%
90%
80%
View Article Online
DOI: 10.1039/C9CC00987F
N
N
N
N
N
N
3ha
: 95%
R
3ga
: 97%
3fa
0
H
O
S
N
N
N
O
O
O
NC
Control experiments indicated that both visible light,
a
NC
a,c
a
3io
: 90%
3bb
3bc
: 93%
: 87%
photocatalyst and a nickel catalyst were all critical for this
transformation (entries 2-4). The reaction performed under an
aerobic atmosphere also did not yield any coupling product (entry
5). Varying the reaction solvent did not improve the result; among
the solvents used, CH3CN delivered the coupling product in 58%
yield (entry 6). Other nickel salts also gave comparable yields (entry
7), but the lower cost of NiCl2•6H2O makes it a better choice.24
Lowering the loading of CdS led to a dramatic decrease in efficiency
(entry 8). The addition of the widely used bipyridine ligand had a
negative effect on the efficiency of coupling reactions (entry 9). To
our surprise, the base DABCO (entry 10), which was necessary in
the dual Ir/Ni catalyst system, was found to completely inhibit the
reaction.
With the optimized conditions in hand, we started to evaluate
the generality of this C-N coupling reaction (Scheme 2). As expected,
the reaction with a series of substituted aryl bromides bearing a
range of synthetically useful functional groups, such as cyano, nitro,
ketone and ester moieties, proceeded well to furnish products 3ba-
3fa in 62-98% yields. Heteroaryl bromides, such as pyrimidine and
pyridine, were also suitable for this transformation, delivering the
corresponding products 3ga and 3ha in 97% and 95% yield,
respectively. Next, a variety of primary and secondary amines were
found to be successful in this heterogeneous C-N coupling protocol.
O
3bd: 94%a
a
R=
R=
H
N
R
3bf
: 94%
R=
R=
a
3be
: 89%
a
NC
3bg
: 73%
OMe
OMe
OMe
OMe
a
a
a
b
R=
3bl
3bh
: 96%
: 91%
: 95%
: 85%
R=
R=
F
F
a
a
Ph
3bi
3bj
: 95%
: 83%
R=
R=
OH
3bm
3bn
n-hexyl
R=
a
3bk
: 81%
R=
NH
Reaction conditions: the same with entry 1 in Table 1; isolated yields. aPerformed
with DBU (2.0 mmol, 2.0 equiv.) at 55 oC. bPerformed with DBU (4.0 mmol, 4.0
equiv.) at 55 oC. cUsing aryl iodide instead of aryl bromide.
Scheme 2 Scope of the C-N coupling reaction
In most cases, 2.0 equiv. of DBU and an elevated reaction
temperature were helpful to ensure the full conversion of aryl
bromides. For example, piperidine and 1,2,3,4-tetrahydro-
isoquinoline were converted to the corresponding aniline
derivatives 3bb and 3bc in 93% and 87% yield, respectively.
Moreover, the direct use of amine hydrogen chloride salt and
excess base were also successful, delivering the fluoride-bearing
product 3bh in good yield. Amines with functional groups, such as
alkene and acetal, were well tolerated, delivering the desired
products 3bk and 3bl in 81% and 96% yield, respectively.
Interestingly, when aminoalcohol was used, chemoselective N-
arylation occurred to produce an N-aryl amino alcohol 3bm in 91%
yield. The coupling reaction with tryptamine also resulted in the N-
aryl product 3bn with the nitrogen atom in the indole ring
untouched. In addition to reactions with amines, the C-N coupling
reaction with a sulfonamide also proceeded well. For instance,
when methyl 4-iodobenzoate and p-toluenesulfonamide were
subjected to standard conditions, the desired product 3io was
prepared in 90% yield. During the performance of C-N coupling
reactions, we noticed that the photocatalyst was attracted to the
surface of the magnetic stirrer (Figure S1, a-c). Then, we separated
the CdS catalyst by simply removing the solution of crude product
and then added Ni salt, aryl bromide, amine and DMA again to
restart this C-N coupling reaction.25 The CdS photocatalyst shows
the same efficiency even after 10 cycles (Figure S1, a-c).
Table 1 Condition optimization for C-N couplinga
CdS (20 mol%)
NiCl2•6H2O (5 mol%)
Br
H
+
N
N
DMA, 6 W blue LEDs
rt, 24 h
F3C
F3C
1a
2a
3aa
entry
variation from the standard conditions
yield (%)b
1c
2
none
83
0
no CdS
3
no NiCl2·6H2O
0
4
in the dark
0
5
in the air
0
6c
MeCN instead of DMA
NiCl2·glyme instead of NiCl2·6H2O
2 mol% of CdS
58
80
12
56
trace
7
8
9
5 mol% dtbbpy as ligand
2.0 eq. DABCO as base
10
aConditions: 1a (1.0 mmol), 2a (2.0 mmol, 2.0 equiv.), CdS (0.2 mmol,
Inspired by the success of the C-N coupling reaction, we next
chose to explore the heterogeneous C-O coupling reaction.26 As
highlighted in Scheme 3, a variety of functional groups on the
benzene ring, such as cyano, ketone, ester and sulfone, in the para
position were tolerated, giving corresponding products 5ca-5ja in
92-96% yields. Variation in substituent position was also compatible
20 mol%), NiCl2•6H2O (0.05 mmol, 5 mol%), and DMA (3.0 mL) under
b
c
irradiation with 6 W blue LEDs. Isolated yield of 3aa. No reaction
occurred in other solvents, such as THF, DCM and CHCl3. DMA: N,N-
Dimethylacetamide; dtbbpy: dtbbpy
bipyridine; LEDs: light-emitting diodes.
=
4,4’-di-tert-butyl-2,2’-
2 | J. Name., 2015, 00, 1-3
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with the dual catalyst system, delivering the desired products 5ka
and 5la in high yields. Naphthyl and quinolyl ether, 5ma and 5na,
can also be produced in high yields under standard conditions.
Given the great value of deuterium labeling in organic synthesis and
the pharmaceutical industry,27 we applied deuterated methanol in
this C-O coupling reaction; the deuterium atom was incorporated
into the product 5bb with 70% yield (fully labelled methyl group).
Moreover, many other alcohols, such as ethanol (5bc), n-pentanol
(5bd), and fluoride-containing alcohol (5be) also reacted well with
4-bromobenzonitrile, delivering the desired products in 88-97%
yields. The coupling reaction with isopropyl alcohol was also proven
to be successful, albeit in a moderate yield (5bh, 54% yield). At the
current stage, aryl bromides with electron-neutral and electron-rich
substituents, as well as aniline, phenol and their analogs cannot
participate in these C-N and C-O coupling reactions for unknown
reasons. To our delight, brief condition optimization successfully
provided the hydroxylated products 6b and 6e in high yields (eq.
1).26 Different from previous reports, noble metal Ir-based
photocatalysts17a and a special amino-containing bipyridine ligand28
are not required in our case.
alternative and competitive choice featuring mild reaction
conditions, easy operations and inexpensive catalysts.
View Article Online
DOI: 10.1039/C9CC00987F
Based on previous reports16-18 and our experimental results, we
proposed a plausible mechanism for the C-N and C-O coupling
reactions of aryl bromides with amines, alcohols or water. As
depicted in Scheme 4, oxidative addition of aryl bromides by a Ni(0)
catalyst delivers an aryl Ni(II) species A, which is converted to
another aryl Ni(II) intermediate B via ligand exchange with amines,
alcohols or water. Meanwhile, heterogeneous photocatalyst CdS is
excited by visible light. The oxidizing holes in the valence band (VB)
of photoexcited CdS would abstract an electron from the Ni(II)
species B to afford the Ni(III) species C, which is believed to be
energetically favored to proceed with reductive elimination and
produce the desired aryl amines, ethers and phenols. Finally, the
conduction band (CB) of photoexcited CdS would reduce the Ni(I) to
complex D to the active Ni(0) species by providing an electron,
thus finishing the heterogeneous dual catalysis cycle.
Ar
LnNiII
Ar Br
Br
2 4
/
(
)
XH
R
A
or H2O
LnNi0
Br-
HBr
CB
Ac
OMe
NC
OCX3
EtO2C
OMe
e
SET
Ar
Ni Catalytic Cycle
R
5ba/5bbb: X=H/D: 96/70%
5ca: 92%
5ja: 94%
5ea: 96%
LnNiII
X
visible light
Ac
O
B
CdS Photoctatlysis
S
OMe
Ph
OMe
OMe
OMe
Br
O
SET
LnNiI
5fa: 93%
5la: 98%
5ka: 93%
Br
OMe
VB
OMe
Ar
D
O
R
h
SET
LnNiIII
Br
X
e
3 5
Ar
/
N
e
X
O
C
R
5ma: 98%
5na: 94%
5bc, R= Et:
97%
5bf, R= Bn:
97%b
Scheme 4 Proposed mechanism for the C-N/C-O coupling
5bd, R= n-C5H9: 88%b
5bd, R= furan-2-ylmethyl: 88%
54%b
5bc, R= i-Pr:
NC
O
R
5bc, R= CF3CH2: 96%
In conclusion, we have developed practical C-N and C-O
coupling reactions of aryl halides with amines and alcohols through
heterogeneous visible light photoredox and nickel dual catalysis.
This protocol represents an alternative and competitive method to
1
2
Reaction conditions: (1.0 mmol), alcohol (2.0 mL), CdS (0.05 mmol, 5 mol%),
NiCl2•6H2O (0.06 mmol, 6 mol%), dtbbpy (0.02 mmol, 2 mol%), Et3N (2.0 mmol,
2.0 equiv.), and DMA (1.0 mL) under irradiation with 6 W blue LEDs; isolated
yields. bAlcohol (5.0 equiv.) and DMA (3.0 mL) were used.
prepare aryl amines and ethers, compared with
a dual
Scheme 3 Scope of the C-O coupling reaction
homogeneous Ir/Ni catalyst system. In this work, only readily
available and much less expensive CdS and nickel salts are required
and this heterogeneous photocatalyst can even be reused many
times. We believe that this dual catalysis strategy utilizing cheap
and recyclable heterogeneous photocatalysts and inexpensive
transition metals would make organic synthesis more practical and
sustainable for industrial production.
CdS (20 mol%)
NiCl2•6H2O (5 mol%)
Br
OH
+
H2O
(1)
DBU (2.0 equiv.), DMA, 55 o
6 W blue LEDs
C
R
R
1b
1e
6b
6e
, R= CN
, R= CO2Et
, R= CN: 85% yield
, R= CO2Et: 87% yield
10.0 equiv.
CdS (10 mol%)
NiCl2•6H2O (2.5 mol%)
Br
H
N
N
+
+
(2)
3 W blue LEDs (two)
DMA, rt, 48 h
NC
NC
3ba
2a
: 2.0 equiv.
: 3.4 g, 98% yield
OMe
1b
: 20 mmol
Br
We are grateful to the National Science Foundation of China
(No. 21822103, 21820102003, 21772052, 21772053, 21572074
and 21472057), the Program of Introducing Talents of
Discipline to Universities of China (111 Program, B17019), the
Natural Science Foundation of Hubei Province (2017AHB047)
and the International Joint Research Center for Intelligent
Biosensing Technology and Health for support of this research.
CdS (5 mol%)
NiCl2•6H2O (6 mol%)
dtbbpy (2 mol%)
MeOH
(3)
Et3N (2.0 equiv.), DMA
3 W blue LEDs (two)
5ba
: 5.9 g, 89% yield
rt, 48 h
NC
NC
1b
4a
: 50 mmol
(excess)
To emphasize the practicability of this heterogeneous
catalysis system, we performed two scale-up reactions. As a
result, the C-N coupling product can be achieved in 98% yield
on a 20 mmol scale with half loading of catalysts, and the C-O Notes and references
coupling reaction can be scaled up to 50 mmol with 89% yield
(eq. 2 and 3). Compared with traditional methods, this
heterogeneous photoredox/Ni catalysis system offers an
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Table of Contents Entry
 no noble metal
 mild conditons  recyclable PC
R1 NH2
or
Br
R2 OH
+
Ar
e-
or
H2O
Ni
CdS
H
N
R1
or
O
R2/H
h+
Ar
Ar