Rh(III)-Catalyzed N-Nitroso Directed C-H Arylation for Facile Construction of Diverse N-Hetero Biaryl Compounds

Article abstract of DOI:10.1002/asia.202000949

A Rh(III)-catalyzed C?H arylation reaction of N-nitrosoanilines has been developed in which arylboronic acids were used as arylation reagents. It provides an efficient strategy for the synthesis of N-nitroso-[1,1′-biphenyl]-2-amine, which is an important starting material for the synthesis of N-hetero biaryl compounds, such as 2-amine-1,1′-biphenyl, carbazole, phenanthridone. This protocol can be applied to various N-alkyl substituted N-nitrosoanilines and N-nitrosoanilines with substituents on the phenyl ring. Arylboronic acids with both electron-donating and electron-withdrawing groups are tolerated.

Full text of DOI:10.1002/asia.202000949

CHEMISTRY
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Accepted Article
Title: Rh(III)-Catalyzed N-nitroso Directed C-H Arylation for Facile
Construction of Diverse N-hetero Biaryl Compounds
Authors: Pei-Long Wang, Yan Wang, Yan Li, and Xi-Sheng Wang
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Chemistry - An Asian Journal
10.1002/asia.202000949
COMMUNICATION
Rh(III)-Catalyzed N-nitroso Directed C-H Arylation for Facile Con-
struction of Diverse N-hetero Biaryl Compounds
Pei-Long Wang,+,[a][b][c] Yan Wang,+,[a] Yan Li*,[a] and Xi-Sheng Wang*,[a]
Dedication ((optional))
Abstract: A Rh(III)-catalyzed C-H arylation reaction of N-nitrosoan-
ilines has been developed in which arylboronic acids were used as
arylation reagents. It provides an efficient strategy for the synthesis
of N-nitroso-[1,1'-biphenyl]-2-amine, which is an important starting
material for the synthesis of N-hetero biaryl compounds, such as 2-
amine-1,1'-biphenyl, carbazole, phenanthridone. This protocol can be
applied to various N-alkyl substituted N-nitrosoanilines and N-nitro-
soanilines with substituents on the phenyl ring. Arylboronic acids with
both electron-donating and electron-withdrawing groups are tolerated.
hydrazines, acridones, oxadiazoliums,[5] pyridoindolobenzaze-
pines, and etc.[6] Since the first example of C-H functionalization
of N-nitrosoanilines by Zhu in 2013,[7] a few examples catalyzed
by rhodium,[8] palladium[9] and cobalt[10] have been developed ac-
cordingly. As one part of our continuous efforts to develop novel
C-H functionalization methods for facile construction of heterocy-
cles,[11] we hence report a rhodium-catalyzed C-H arylation of N-
nitrosoanilines. This method has demonstrated broad substrate
scope, good functional group tolerance and mild conditions. The
synthetic potential of this transformation has been well elaborated
through various further transformations to diverse N-hetero biaryl
compounds and N-heterocycles,[12,13] which are ubiquitous struc-
In the past several decades, transition-metal-catalyzed C-H acti-
vation reaction has emerged as a powerful tool for the synthesis
of useful organic molecules in an atom and step-economical
way.[ Considering there are always large number and various
kinds of C-H bonds in one organic molecule, to selectively activate
the C-H bond in a special position is a rather important issue. Ac-
cordingly, the introduction of directing groups into the target mol-
ecules has been widely used as the most effective strategy for
solving this problem.[2] Indeed, the generally used directing
groups are heteroatom-containing functional groups, which selec-
tively activate the C-H bond that is most close to the metal center
through coordination with the metal. Not only the site selectivity
control, but also the low reactivity of the transition-metal catalysts
could be well resolved by this directing group strategy. As results,
many functional groups have been developed as directing groups,
and applied successfully in C-H activation reactions. However,
the extra steps for installation and removal of the directing groups
would definitely reduce the step- and atom-economy of these C-
H functionalization reactions. To address this issue, the develop-
ment of easily removable or transformable directing groups to re-
alize diverse metal-catalyzed C-H activations has attracted in-
creasing attentions in the past years.
[14]
tural motifs found in many bioactive compounds and materials.
We initiated our study by using N-ethyl-N-nitrosoaniline (1a) as
the model substrate and phenylboronic acid (2a) as the coupling
1]
partner in the presence of a catalytic amount of [Cp*RhCl
mol%) as a catalyst in 1,4-dioxane at 120 °C for 20 h. While the
reaction was performed with Ag CO used as the oxidant, to our
2 2
] (2.5
2
3
delight, the desired arylation product 3a was afforded successfully,
albeit in a pretty low yield (9%, entry 1, table 1). Considering the
exchanged anion from the additives has great influence on the
catalytic activity of rhodium catalyst, a careful investigation to the
extra silver additives was next carried out. Indeed, the addition of
2
0 mol% of AgSbF
catalyst [Cp*RhCl
the yield of xx, and so did AgBF
6
, which was commonly used for activating the
as an additive, gave none of improvement for
and AgOAc (entries 2-4). To our
2 2
]
4
excitement, further screening revealed that AgOTf was effective
to increase the yield remarkably to 55% (entry 5). To our satisfac-
tory, lowering the reaction temperature to 100 °C could give a
higher yield (68%, entry 6). To further improve the yield, the
screening of oxidant was next performed, which showed that only
2 3
silver salts could promote this reaction effectively, and Ag CO
was still the best choice (entries 7-12). Meanwhile, the following
screening of solvents indicated that the ethers, including 1,4-diox-
ane, THF and THP, gave the better results, and THF afforded the
best
N-nitrosoanilines served widely as an important kind of bio-
logically active compounds in biological and pharmaceutical
chemistry, and have been studied intensively in different research
areas.[3] Considering N-nitrosoanilines could be easily prepared
in one step from anilines,[4] they are widely existing as a class of
useful synthetic intermediates, which would afford various syn-
thetically useful compounds through different kinds of transfor-
mations. Actually, N-nitrosoanilines could be converted to amines,
R
1
R
1
B(OH)2
N
NO
N
Rh(III)
R
2
NO
R
2
+
R
3
R
3
[a]
Department of chemistry, University of Science and Technology of
China, 96 Jinzhai Road, Hefei, Anhui 230026, Peoples Republic of
China
R
1
R
1
R
1
NH
N
O
N
E-mail: liyan08@ustc.edu.cn; xswang77@ustc.edu.cn
Department of chemistry, Huaibei Normal University, 100 Dongshan
Road, Huaibei, Anhui 235000, Peoples Republic of China
Information College, Huaibei Normal University, 100 Dongshan
Road, Huaibei, Anhui 235000, Peoples Republic of China
These authors contributed equally to this work.
R
2
R
2
R
2
[
b]
c]
R3
R3
R3
[
[+
]
Scheme 1. Rh(III)-Catalyzed C-H arylation of N-nitrosoanilines.
Supporting information for this article is given via a link at the end of
the document.
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Chemistry - An Asian Journal
10.1002/asia.202000949
COMMUNICATION
Table 1. Optimization of the reaction conditions.[a][b]
Table 2. Arylation of N-nitrosoanilines with arylboronic acids.[a][b]
Et
N
R2
N
Et
N
B(OH)
2
[RhCp*Cl
additive (20 mol%)
2
]
2
(2.5 mol%)
R2
N
B(OH)
2
[RhCp*Cl
AgOTf (20 mol%)
2 2
] (2.5 mol%)
NO
NO
NO
+
+
R
1
NO
NO
oxidant (2.0 equiv.), solvent
R
1
R3
Ag CO (2.0 equiv.)
2
3
H
R3
1
20 °C, 20 h
H
THF, 100 °C, 20 h
1
a
2a
3a
1
2
3
entry
additive
-
oxidant
solvent
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
PhCl
yield(%)
Et
N
Et
Et
N
N
1
2
3
4
Ag
Ag
Ag
Ag
Ag
Ag
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
3
3
3
3
3
3
9
12
28
trace
55
68
60
64
10
5
NO
NO
AgSbF
6
Me
Cl
Br
AgBF
4
3b, 45%
3c, 61%
3d, 68%
Et
Et
Et
AgOAc
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
N
N
N
NO
NO
NO
Ph
5
6[c]
Ph
2
SO Me
3
e, 62%
3f, 46%
3g, 54%
7[c]
8[c][d]
9[c]
Ag
CO
AgOAc
Cu(OAc)
Cu(TFA)
Et
Et
2
O
Et
N
N
N
NO
NO
NO
Ag
2
3 2
, Ag O
OMe
MeO
3i, 43%
3
h, 56%
3j, 65%
1
1
1
1
1
1
1
1
0[c]
2
Et
N
Me
Me
N
1[c]
N
2
0
NO
NO
NO
2[c]
3[c]
4[c]
5[c]
6[c]
7[c]
K
O
2 8
0
2
S
S
N
Ag
Ag
Ag
Ag
Ag
Ag
Ag
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
3
3
3
3
3
3
3
13
40
0
3l, 68%
3m
, NR
3
k, trace
acetone
Me
N
i-Pr
n-Bu
N
N
MeCN
NO
NO
NO
THF
70
55
75(73)[f]
0
Br
Br
Br
THP
3n, 69%
3o, 72%
3p, 63%
Me
N
Me
Me
N
1
8[c][e]
THF
N
NO
NO
NO
1
9[c][e][g]
THF
Me
Cl
Br
Ph
Ph
Ph
[
a] Reaction conditions: 1a (0.2 mmol), 2a (0.6 mmol, 3 equiv), [Cp*RhCl
mol%), AgOTf (20 mol%), oxidant (2.0 equiv), solvent (1.5 mL) at 120 ˚C for 20
h. [b] yield was determined by 1H NMR using CH
Br as internal standard. [c]
00 ˚C. [d] 1 equivalent of Ag CO and 1 equivalent of Ag O were used. [e] 20
mol% of AgOTf was used. [f] isolated yield. [g] without [Cp*RhCl
2 2
] (2.5
3
q, 75%
3r, 71%
3s, 66%
Me
N
Me
Me
N
2
2
N
Me
1
2
3
2
NO
NO
NO
2 2
] .
MeO
NC
yield to 70% (entry 16). It is worth noting that increasing the load-
ing of AgOTf from 10 mol% to 20 mol% had a positive effect on
the reaction, giving the arylation product 3a in 73% isolated yield
Ph
Br
Br
3
t, trace
3u, trace
3v, 68%
Me Me
N
N
N
NO
(
entry 18). Lastly, a control experiment in the absence of rhodium
NO
catalyst afforded none of the desired product 3a (entry 19).
With the optimized reaction conditions in hand, we next tried to
expand the scope of the aryl boronic acids and N-nitrosoanilines
Br
Br
Br
3
w, NR
3x, 25%
3y, NR
(
Table 2). As shown in Table 2, a variety of arylboronic acids bear-
[
a] Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol, 3 equiv), [Cp*RhCl
2
]
2
(2.5
ing both electron-donating and electron-withdrawing groups were
well tolerated, affording the corresponding products 3 in moderate
yields generally (3b-3i). Compared with the N-nitrososnilines, the
substituted position on the phenyl ring of arylboronic acids has
only relatively slight effect on the yield (3h and 3i). Not surprisingly,
halogen substituents, including chloro and bromo, were also well
compatible with this catalytic system to give the arylated biaryls
mol%), AgOTf (20 mol%), Ag
h. [b] isolated yield.
2 3
CO (2.0 equiv), THF (1.5 mL) at 100 ˚C for 20
(
3c, 3d), which could be used for further transformations to other
useful compounds through known transition-metal catalyzed cou-
pling reactions. 2-Naphthaleneboronic acid was coupled to N-
ethyl-N-nitrosoaniline smoothly (3j), but 1-naphthaleneboronic
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Chemistry - An Asian Journal
10.1002/asia.202000949
COMMUNICATION
acid failed (3k) caused possibly by the steric hindrance. Addition-
ally, the heteroarylboronic acids were also investigated. Compar-
ing with thiophene-3-boronic acid gave the corresponding product
in 68% yield (3l), the reaction with pyridine-3-boronic acid cannot
proceed (3m) for its strong coordination ability to palladium cata-
lyst. Subsequently, we then expanded the scope of N-nitrosoan-
ilines, which disclosed that a variety of N-nitrosoanilines were ar-
ylated smoothly to furnish the corresponding N-nitroso biaryla-
mines in good to moderate yields. To our satisfactory, a series of
N-alkyl protecting-groups, including methyl, ethyl, n-butyl and i-
propyl, on the N-nitrosoanilines could be well tolerated in the re-
action conditions, and the steric hindrance of the alkyl group has
no obvious influence on this transformation (3n-3p). The investi-
gation of the electronic effect on the phenyl ring revealed that
moderate electron-donating (3q) and -withdrawing groups (3r, 3s)
were suited in this arylation. However, the substrates bearing
strong electron-donating (3t) and -withdrawing groups (3u) gave
only trace amount of the corresponding products. The examina-
through reported methods. As shown in Scheme 2, an oxidative
palladium-catalyzed amination of C-H bond afforded the desired
carbazole at ambient temperature in 81% yield.[12a] Meanwhile, a
palladium(II)-catalyzed C-H carbonylation of biaryl-2-amine 4 pro-
ceeded smoothly to furnish the corresponding phenanthridone 6
in high yield. [13a]
In summary, we have developed a Rh(III)-catalyzed, N-nitroso
directed C-H arylation reaction employing arylboronic acids as ar-
ylation reagents. A wide range of functional groups such as bromo,
chloro, methoxy, phenyl, sulphonate groups were compatible with
this reaction condition. While the nitroso group could act as a
good transformable directing group, the synthetic potential of this
method has been well demonstrated by facile construction of di-
verse N-hetero biaryl compounds, including [1,1'-biphenyl]-2-
amine, carbazole, and phenanthridone, using the arylation
products as useful precursors for varous further transformations.
tion of substituent’s effect on the phenyl ring of N-nitrosoanilines Experimental Section
showed that both meta- and para-substituted substrates were
compatible with this catalytic reaction, but the ortho-substituent
3w) was incompatible. Only less-hindered ortho-C-H bond on the
General procedure for the Rh(III)-catalyzed arylation of N-nitrosoanilines:
(
phenyl ring could be arylated successfully for the meta-substi-
tuted substrates (3v). Both results demonstrated the obvious ste-
ric influence on this transformation brought by the substituents on
the phenyl ring. At last, it was noteworthy to mention that N-nitrso-
tetrahydroquinoline was transformed to 8-arylquinoline directly in
this reaction system, in which the desired C-H arylation followed
by denitrosation and dehydro-aromatization proceeded in a se-
quence (3x). In contrast, no reaction took place when the similar
In a 35 mL oven-dried sealed tube, N-nitrosoaniline 1 (0.2 mmol), aryl-
boronic acid 2 (0.6 mmol), [Cp*RhCl (3.1 mg, 2.5 mol%), AgOTf (10.3
mg, 20 mol%), Ag CO (110.3 mg, 2 equiv), THF (1.5 mL) were added in
sequence. The tube was then sealed with a Teflon lined cap and placed
into a preheated oil bath at 100 °C with vigorous stirring. 20 hours later,
the reaction mixture was cooled to room temperature. 10 mL ethyl acetate
was added and the resulting mixture was filtered through a plug of silica
2 2
]
2
3
(eluted with EtOAc). The solvent was evaporated to dryness under re-
duced pressure and the residue was purified by flash column chromatog-
1-nitrosoindoline was used as substrate (3y), that might be due to
raphy to give product 3.
inappropriate angle of the directing group caused by the rigid five-
membered ring.
To demonstrate the synthetic potential of this N-nitroso directed
arylation reaction, the resulted N-nitroso biarylamines were next
tried to be transformed to diverse N-hetero biaryl compounds and
N-heterocycles. As shown in Scheme 2, the nitroso group could
be deprotected smoothly in the presence of iodine (0.5 equiv) and
triethylsilane (3.0 equiv) in dichloromethane solution at room tem-
perature, affording the corresponding 2-ethylamino-1,1’-biphenyl
Acknowledgements
We gratefully acknowledgethe Anhui Provincial Natural Science
Foundation (No. 1808085QB29) and Key Project of Provincial
Natural Science Research Foundation of Anhui Universities,
China (No. KJ2018A0675), the National Science Foundation of
China (21971228, 21602213) for financial support.
4
in 93% yield.[14] As an important synthetic intermediate for fur-
ther derivations, biphenyl 4 could be used for further cyclization to
produce N-heterocycles
Keywords: N-nitrosoaniline • arylboronic acid • rhodium • C-H
activation • arylation
Et
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Pd(OAc)
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(1.2 equiv.)
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toluene, rt
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TFA (2 equiv.)
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Chemistry - An Asian Journal
10.1002/asia.202000949
COMMUNICATION
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Pei-Long Wang, Yan Wang, Yan Li ,* Xi-
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Rh(III)-Catalyzed N-nitroso Directed
C-H Arylation for Facile Construction
of Diverse N-hetero Biaryl Com-
pounds
A Rh(III)-catalyzed C-H arylation reaction of N-nitrosoanilines was developed in which arylboronic acids were used as arylation reagents.
N-nitroso was used as a transformable directing group. The product N-nitroso-[1,1'-biphenyl]-2-amine can be used for the synthesis of
diverse N-hetero biaryl compounds, such as [1,1'-biphenyl]-2-amine, carbazole, phenanthridone.
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