Copper-Catalysed Electrophilic Amination of Aryl(alkenyl) Boronic Acids with Nitrogen-Containing Hypervalent Iodine (III) Reagent

Article abstract of DOI:10.1002/adsc.202100594

A copper-catalysed electrophilic N-imination of aryl(alkenyl) boronic acids with a stable hypervalent iodine(III) reagent containing a transferable (diarylmethylene)amino group is developed. The electrophilic C?N cross-coupling reaction proceeds smoothly at room temperature under oxidant-free and base-free conditions, which is further characterized by the broad functional group compatibility, thereof, extending the N-electrophile scope of electrophilic C?N cross-coupling outside the limitation of N?O and N?Cl reagents. (Figure presented.).

Full text of DOI:10.1002/adsc.202100594

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doi.org/10.1002/adsc.202100594
Copper-Catalysed Electrophilic Amination of Aryl(alkenyl)
Boronic Acids with Nitrogen-Containing Hypervalent Iodine (III)
Reagent
Yuanyuan Hu,a Songlin Zheng,a Wu Fan,b,* and Weiming Yuana, c,*
a
Key Laboratory of Material Chemistry for Energy Conversion and Storage
Ministry of Education
Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica
School of Chemistry and Chemical Engineering
Huazhong University of Science and Technology (HUST)
1037 Luoyu Road, Wuhan 430074, People’s Republic of China
E-mail: yuanwm@hust.edu.cn
b
Key Laboratory of Tobacco Flavor Basic Research
Zhengzhou Tobacco Research Institute of CNTC
No. 2 Fengyang Street High-Tech Zone, Zhengzhou 450001, People’s Republic of China
E-mail: fanwu2015@126.com
Guangdong Provincial Key Laboratory of Catalysis
c
Southern University of Science and Technology
Shenzhen 518055, People’s Republic of China
Manuscript received: May 17, 2021; Revised manuscript received: August 2, 2021;
Version of record online: August 19, 2021
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202100594
and till now still remains a particularly vibrant topic of
Abstract: A copper-catalysed electrophilic N-imi-
nation of aryl(alkenyl) boronic acids with a stable
research. Among them, transition-metal-catalysed CÀ N
bond cross-couplings predominated owing to the
hypervalent iodine(III) reagent containing a trans-
obvious advantages such as high efficiency, good
ferable (diarylmethylene)amino group is developed.
selectivity, mild condition, broad substrate scope and
The electrophilic CÀ N cross-coupling reaction
proceeds smoothly at room temperature under
oxidant-free and base-free conditions, which is
further characterized by the broad functional group
compatibility, thereof, extending the N-electrophile
scope of electrophilic CÀ N cross-coupling outside
the limitation of NÀ O and NÀ Cl reagents.
functional group compatibility and so on.[2] Classical
CÀ N bond cross-couplings involving carbon electro-
philes and nitrogen nucleophiles, typified by the well-
known Ullmann-Goldberg[3] and Buchwald-Hartwig[4]
reaction and have been largely extended by many
others (Scheme 1a).[5] In contrast, the coupled of
carbon nucleophiles and nitrogen nucleophiles to form
CÀ N bonds in the aid of external oxidants and copper
catalyst or stoichiometric amount of Cu(II) salts, now
termed as Chan-Lam reaction, provides an alternative
yet robust approach to metal-catalysed CÀ N bond
cross-coupling (Scheme 1b).[6]
Keywords: CÀ N bond cross-coupling; Boronic
acids; Hypervalent NÀ I reagent; Copper catalysis;
Umpolung amination
Despite of the significant progress achieved in this
excited field, some obstacles still persist. For example,
The formation of CÀ N bonds ranks as one of the most Buchwald-Hartwig reaction typically need expensive
important and widely practiced reactions in synthetic transition metal catalysts ligated with structurally
chemistry due to the fact that amines and their complex ligands, elevated temperature and bases and
derivatives are prevalent motifs in numerous natural additives to promote. Conversely, Chan-Lam amination
products and pharmaceutical targets.[1] As a conse- could allow CÀ N bond formation to proceed smoothly
quence, many efforts have been devoted to the under much milder conditions (room temperature,
development of highly efficient and synthetically weak base and ambient atmosphere) and obviate to use
practical methods for the construction of CÀ N bonds the expensive catalysts/ligands. However, a stoichio-
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sulfonyl oximes could react with RMgX or RZnX to
afford N-substituted benzophenone imines in the
presence of Cu(I) catalyst. Later on, Johnson[11] and
Jarvo[12] and co-workers independently reported Cu or
Ni-catalysed electrophilic amination of diorganozinc
reagents with O-acyl hydroxylamines or N-chloro-
amines, respectively. Compared with Grignard and
organozinc reagents, organoborons are a kind of read-
ily available, non-basic, less-toxic and widely compat-
ible organometallic species, which have been widely
investigated in copper-mediated/catalysed CÀ N oxida-
tive cross-couplings (Chan-Lam reaction). In the past
decade, aryl boronic acids and their derivatives have
also been explored in umpolung aminations with
electrophilic R2N+ synthons by Liebeskind,[13] Lei,[14]
Miura,[15] Kitamura[16] et al. Although a wide range of
R2N+ synthons have been disclosed for umpolung
amination, however, the most reported electrophilic
amination reagents are largely limited to the reactive
and air- and moisture-sensitive hydroxylamines and N-
chloroamines. Utilization of those reactive N-electro-
philes hampered the synthetic practicability and opera-
tional convenience, thus, further exploring novel and
stable R2N+ synthons for catalytic electrophilic amina-
tion are of high interesting.
Hypervalent iodine (III) reagents containing a
benziodoxolone skeleton have emerged as versatile
and environmentally benign reagents for organic
chemistry, which are potent atom-transfer reagents and
mild oxidants with a good stability to air and
moisture.[17] Hypervalent iodine reagents containing a
Scheme 1. Previous studies and our proposal of electrophilic
CÀ N cross-coupling of boronic acids and hypervalent NÀ I
reagent.
metric amount of external oxidant is necessary for this NÀ I bond have been intensively studied in CÀ H bond
oxidative cross-coupling.
oxidative amination,[18] however, they have rarely been
In particular, in both catalytic systems, N-nucleo- used in transition metal-catalysed CÀ N bond cross-
philes are used as nitrogen sources, which commonly coupling reactions. Due to the importance of CÀ N
possesses a strong nucleophilicity and basicity could bond forming events and the superiority of hypervalent
potentially undergo unfavourable competitive coordi- NÀ I reagent over other electrophilic aminating re-
nation to transition metals, thereby leading to a agents, we envisioned that the hypervalent NÀ I reagent
decrease of catalyst activity. Besides, the basic con- might be used as a mild yet robust electrophilic
dition somewhat restricts the functional group compat- aminating reagent in copper-catalysed electrophilic
ibility.
CÀ N cross-couplings (Scheme 1d). Here, we reported
Umpolung strategy represents a powerful and our recent discovery.
complementary approach for bond forming events,
To test the feasibility, we synthesized (diarylmeth-
which would not otherwise be possible or difficult-to- ylene)amino-substituted cyclic benziodoxolone reagent
access due to the electronic mismatch issues.[7] 2a[19] and commenced our reaction with p-tolylboronic
Umpolung reactions often showcase superior reactivity acid 1a in the presence of a catalytic amount of
and selectivity compared to the normal polarity Cu(OTf)2 in MeCN at room temperature (Table 1). To
patterns. In this regard, the effective applications of the our delight, after 4 hours, the reaction preliminarily
umpolung strategy in CÀ N bond cross-couplings are of delivered the desired product N-(p-tolyl)benzophenone
highly valuable and have received increasing attention imine 3a in 14% yield (Entry 1). This initial success
during the past decades (Scheme 1c),[8] where the inspired us to further investigate other reaction param-
reaction of electrophilic nitrogen sources with nucleo- eters. Solvent screening showed that DCM was the
philic carbon sites is thus complementary to Buch- best, while polar solvents such as DMF and THF
wald-Hartwig and Chan-Lam amination for catalytic completely retarded the reaction (Entries 2–5). Other
CÀ CN bond formation under very mild, non-basic and copper salts such as CuBr2, CuI or CuCl gave a
oxidant-free conditions. Early studies from Erdik[9] and comparable yield (Entries 6–8). Pleasingly, CuBr and
Narasaka[10] et al. reported that the electrophilic O- Cu(CH3CN)4PF6 could increase the yield up to 60%
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Table 1. Optimization of reaction conditions.[a]
groups like F, Cl, Br, and CF3 (3o–3r). These highly
valued functional groups provided a good platform for
further synthetic modifications. 2-Naphthylboronic
acid reacted with a moderate yield (3s). Heteroarylbor-
onic acids could also react well under the standard
conditions (3t–3u). Apart from arylboronic acid,
alkenyl boronic acid could also be able to participate
the cross-coupling reaction, and delivered the syntheti-
cally useful 2-azadiene in a comparable yield (3v–
3w). Finally, we further investigated the substitution
effect on aryl ring of hypervalent NÀ I reagent and the
results shown that both electron-rich and electron-poor
substituents were well tolerated (3x–3y). Unsymmetric
substrate with 1:1 ratio of Z/E isomer delivered the
product in a mixture form of Z/E isomer (1:1) in 44%
yield
(3z).
Unfortunately,
Zhdankin’s
amidobenziodoxole[20] and phthalimidate-based hyper-
valent iodine reagent[18d] are not suitable for this
transformation (not shown, see SI). It should be noted
that in each individual case, N-protected imine product
can undergo hydrolysis to get benzophenone in a range
of 10~20% yield.
To get more insights into the mechanism of this
copper-catalysed CÀ N bond formation reaction, a
series of mechanistic experiments were performed:
First, MesCu complex was synthesized according to
and 58% (Entries 9–10), respectively. Water had a reported procedure[21] and a stoichiometric reaction of
significant influence on the efficiency, when 1.5 MesCu with 2a gave 40% yield of coupling product
equivalents of H2O was added to the reaction system 3aa (Scheme 3, Eq. 1). This result suggested that
and meanwhile adjusted the molar ratio of 1a:2a to arylcopper arising from the transmetallation of arylbor-
1.5:1, the yield could be further elevated to 76% onic acid with Cu(I) might be an active intermediate
(Entry 11). We proposed that water facilitated the for the reaction. The reaction of 1a and 2a with a
transmetalation step of arylboronic acid with copper catalytic amount of MesCu also proceeded smoothly,
salt. Control experiment indicated that copper catalyst further verified the above conclusion (Eq. 2). More-
is critical to the reaction (Entry 12), and this was over, a stoichiometric reaction of aryl boronic acid
further verified by a series of control experiments: with CuBr was conducted, after 4 hours stirring, the
when other transition metal catalysts such as NiCl2, mixture was quenched by H2O and 1,1’-biphenyl was
PdCl2, AgBF4 etc. was added, the reaction was indeed detected in 23% yield. Extended the reaction
completely suppressed (see SI for details).
time to 20 h, the yield increased up to 44% (Eq. 3).
With the optimized conditions in hand, we studied These results also provided evidence that transmetalla-
the scope of the reaction with respect to various tion intermediate ArCu(I) might involved in the
arylboronic acids (Scheme 2). A variety of substituted system. This preliminary study came to a conclusion
arylboronic acids reacted with 2a to generate the N- diametrically opposed to Lei[14] and Miura’s[15] result.
imination products in moderate to good yields. The After get the answer of transmetallation between
reaction of arylboronic acids containing electron- arylboronic acid and Cu(I) is the initial step, the next
donating group like methyl, methoxy, tert-butyl etc. question is how the oxidative addition of arylcopper
proceeded efficiently to obtain the corresponding with hypervalent NÀ I reagent proceeded. To investigate
products (3a–3f). Electron-deficient substrate reacted whether the oxidative addition step involved a radical
with a somewhat lower efficiency compared to the pathway, radical enquiry experiments were performed.
electron-rich ones. The steric demanding substrates, The standard reaction with 2.0 equiv. of a radical
for example, ortho-methyl substituted arylboronic acid scavenger like 2,2,6,6-tetramethylpiperidin-1-oxyl
led to a large decrease in yield (3g). By taking (TEMPO) or 1,1-diphenylethylene was not inhibited at
advantages of the extremely mild reagents and con- all (Eq. 4). However, when butylated hydroxytoluene
ditions performed, this copper-catalysed electrophilic (BHT) was added, the desired reaction was completely
CÀ N cross-coupling accommodated a broad scope of supressed and BHT-trapped species was detected by
functionalities such as silyl, ester, cyano, ketone, HRMS analysis (Eq. 5). Moreover, the benzophenoni-
aldehyde, nitro, alkene (3h–3n) as well as halogen minyl radical dimerization byproduct was detected by
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Scheme 2. Substrate scope of CuBr-catalysed electrophilic N-imination of aryl(alkenyl)boronic acids.[a]
GC analysis (the standard sample could be obtained by the backbone,[17c,f] thus, other metal-based Lewis acids
literature’s procedure[22]) and further confirmed by were examined for comparison. Indeed, when added
HRMS analysis (Eq. 6). Both reactions suggested that metal salts such as FeCl3, ZnCl2, MgCl2, which are
the oxidative addition step might involve a radical very unlikely to undergo oxidative addition with 2a to
pathway. Furthermore, a stoichiometric reaction of form high valence metal species, various degrees of
hypervalent iodine reagent 2a with CuBr was also decomposition of 2a also happened, despite with a
conducted: 73% of diphenylmethanimine together with relatively low rate. Besides, 2a is quite stable in the
3% of benzophenone were detected once the resulting absence of CuBr (Eq. 8). These experimental results
mixture was quenched by H2O (Eq. 7), this result provided the evidence to support the speculation that
might support the formation of Cu(III) intermediate by the oxidative addition of CuBr to 2a as the initial step
the oxidative addition of Cu(I) to 2a. However, it in the catalytic cycle is indefinite.
should be noted that CuBr can also act as Lewis acid
to coordinate with carbonyl group of 2a to decompose nistic studies, a rational mechanism was proposed in
Based on literature’ reports[13,14,15] and our mecha-
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Scheme 4. Proposed mechanism.
Scheme 4: different from the previous reports on
oxidative addition of Cu(I) to electrophilic aminating
reagent as the initial step, our experimental results
showed that the reaction started from the transmetalla-
tion of arylboronic acid with Cu(I), followed by
oxidative addition with hypervalent NÀ I reagent to
form a putative ArCu(III)N=CR2 intermediate via a
single electron oxidation and radical rebounding path-
way, which intermediate sequentially underwent reduc-
tive elimination to deliver the desired product and
simultaneously regenerated Cu(I) catalyst to complete
the catalytic cycle. Although several evidences indi-
cated that the reaction was triggered by transmetalla-
tion of arylboronic acid with CuBr, an alternative
mechanism through the oxidative addition of a hyper-
valent iodine reagent to Cu(I) followed by a trans-
metalation cannot be completely ruled out at this stage.
In conclusion, we disclosed here an electrophilic N-
imination of aryl(alkenyl) boronic acids with a stable
hypervalent NÀ I (III) reagent in the presence of
catalytic Cu(I) salt. This electrophilic CÀ N cross-
coupling reaction is characterized by its very mild and
simple conditions (room temperature, oxidant and
base-free) and tolerated a variety of functional groups
with moderate to good yields. Of particularly note,
mechanistic studies suggested that the reaction might
be preferably triggered by the transmetallation of
arylboronic acid with Cu(I) followed by oxidative
addition with hypervalent NÀ I reagent, which pathway
is different from that proposed in previous electrophilic
CÀ N cross-coupling involving NÀ O and NÀ Cl re-
agents.
Experimental Section
An oven-dried 10 mL Schlenk tube containing a magnetic stir
bar was charged with hypervalent NÀ I reagent 2a (128 mg,
0.30 mmol, 1.0 equiv.), p-tolylboronic acid 1a (61.2 mg,
0.45 mmol, 1.5 equiv.) and CuBr (4.30 mg, 0.030 mmol,
Scheme 3. Mechanistic studies.
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0.10 equiv.). After evacuated and backfilled with nitrogen three
times, freshly distilled dichloromethane (6.0 mL) was added to
the Schlenk techniques by syringe, then H2O (8.1 μL,
0.45 mmol, 1.5 equiv.) was added by micro syringe, the
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°
resulting mixture was stirred at 25 C under a static pressure of
nitrogen for 4 h. Then, volatiles were removed under reduced
pressure to give the crude product. Purification by flash column
chromatography on prebasified silica (EA/PE with addition of
0.5% NEt3) to give the pure product.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (21702229), Guangdong Basic and Applied Basic
Research Foundation (2019A1515110788), Guangdong Provin-
cial Key Laboratory of Catalysis (Grant No. 2020B121201002),
Innovation Projects of Zhengzhou tobacco research institute
(442020CR0320), the Fundamental Research Funds for the
Central Universities (HUST), and the Innovation and Talent
Recruitment Base of New Energy Chemistry and Device
(B21003) for the financial support. We also thank the Analytical
and Testing Centre of HUST, Analytical and Testing Centre of
the school of Chemistry and Chemical Engineering (HUST) for
data characterizing.
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COMMUNICATIONS
Copper-Catalysed Electrophilic Amination of Aryl(alkenyl)
Boronic Acids with Nitrogen-Containing Hypervalent Iodine
(III) Reagent
Adv. Synth. Catal. 2021, 363, 1–8
Y. Hu, S. Zheng, W. Fan*, W. Yuan*