Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides

Article abstract of DOI:10.1021/acscatal.8b00536

An efficient catalytic system based on a Co(II)-NHC precursor has been developed for the cross coupling of bis(pinacolato)diboron with aryl halides including aryl chlorides, affording the aryl boronates in good to excellent yields. A wide range of functional groups are tolerated under mild reaction conditions. The reaction shows excellent chemoselectivity for bromide over chloride. Preliminary mechanistic investigations show that the catalytic cycle may rely on a cobalt(I)-(III) redox couple.

Full text of DOI:10.1021/acscatal.8b00536

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Efficient Synthesis of Aryl Boronates via Cobalt-
Catalyzed Borylation of Aryl Chlorides and Bromides
Piyush Kumar Verma, Souvik Mandal, and K. Geetharani
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b00536 • Publication Date (Web): 05 Apr 2018
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Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Boryla-
tion of Aryl Chlorides and Bromides
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Piyush Kumar Verma, Souvik Mandal, K. Geetharani*
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India
ABSTRACT: An efficient catalytic system based on a Co(II)-NHC precursor has been developed for the cross coupling of
bis(pinacolato)diboron with aryl halides including aryl chlorides, affording the aryl boronates in good to excellent yields.
A wide range of functional groups are tolerated under mild reaction conditions. The reaction shows excellent chemoselec-
tivity for bromide over chloride. Preliminary mechanistic investigations show that the catalytic cycle relies on a cobalt(I)‒
(
III) redox couple.
KEYWORDS: Boronate esters, Cobalt, C-X activation, N-heterocyclic carbenes, Suzuki–Miyaura
6
e
INTRODUCTION
benzene could be borylated in a poor yield of 5 %. Met-
al-free photoinduced C-X and dual C-H/C-X borylation of
Aryl boronic acids and boronate esters have been rec-
ognized as indispensable building blocks in organic syn-
thesis, particularly in transition-metal-catalyzed cross-
coupling reactions for the formation of various C‒C and
C-heteroatom bonds, owing to their ease of handling,
bench stability, high functional group compatibility and
14
haloarenes were reported by Larionov et al. and pyri-
dine-catalyzed radical borylation of aryl halides was re-
ported by Jiao et al., but only two aryl chlorides have
15
been described in each cases. Very recently, Nakamura
and co-workers reported an iron catalyzed borylation
which can effectively transform the biaryl chlorides into
their corresponding boronate esters in the presence of
KO Bu. Therefore, there remains a strong need to devel-
op cost effective and environmentally benign base-metal
catalysts, in particularly cobalt as catalyst for the boryla-
tion of aryl chlorides. The first cobalt-catalyzed borylation
of aryl halides (including chloro-, bromo-, and io-
doarenes) and pseudohalides was reported in 2016 by Hu,
Huang and co-workers, which typically involve the use of
oxazolinylferrocenylphosphine ligands and MeLi, a reac-
1
low toxicity. Moreover, they have found broad applica-
tions as synthetic intermediates in pharmaceuticals, agro-
chemicals, liquid crystals and organic light-emitting di-
t
6f
1
c
odes. Despite their versatility, the conventional methods
for their synthesis involve aryl lithium compounds or
Grignard reagents which are not compatible with numer-
ous functional groups and are limited by the availability
2
of the organometallic reagents. To expand the scope of
arylboronates, a variety of precious metal catalyst sys-
tems, such as Rh, Re, Ru and especially Ir were developed
over the past decades via direct C–H borylation of arenes.
Complementary, highly selective metal-catalyzed boryla-
16
3
tive organometallic reagent. Herein, we report an active
catalyst composed of cobalt(II) and NHC as ligand that
efficiently converts aryl chlorides to boronate esters un-
der mild reaction conditions.
2
tion reactions of (sp )C–X (X = Cl, Br, I, OTf) bonds have
also been developed.
4
,5
However, the economic con-
strains, low natural abundance and environmental con-
cerns of precious metal catalysts have demanded the
investigation of earth-abundant and inexpensive base
RESULT AND DISCUSSION
NHC supported Co(II)-complex, Co(IMes) Cl (I; IMes
= 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) was
prepared following literature procedure in good yield.
Reaction conditions were optimized using chloroanisole
2
2
6
7
8
9
10
metal alternatives, such as Fe, Co, Ni, Cu, Zn, and
17a
11
even metal-free conditions for the borylation of aryl
halides. The use of aryl iodides or bromides is often nec-
essary, whereas, there are only few reliable methods avail-
able in the literature for the borylation of relatively inex-
pensive and broadly available aryl chlorides.
(2a) as a model substrate by using 5 mol % of I as catalyst,
1
.3 equiv of B pin and a variety of solvents, bases and
2
2
ligands. Among several solvents screened, MTBE (tert-
butylmethyl ether) was found to be superior to other
solvents with 97% yield (Table 1, entries 1-5). Bases other
than KOMe proved inferior (entries 6-10). Weak bases like
Cs CO and KOAc could not produce even trace amount
The aryl chlorides borylation is always challenging, and
there were no methods available for this transformation
until 2001. The first example was reported by Ishiyama et
2
3
1
2
al. using Pd as a catalyst and subsequently scope was
of desired product (entries 9-10). There was no reaction in
the absence of a base (entry 11). Further, influence of the
ligand was studied using ICy (1,3-bis-cyclohexylimidazol-
1
3
expanded by others using mainly Pd and few Ni catalyst
8g-l
systems. In 2014, Bedford et al. reported iron catalyzed
borylation of alkyl, allyl and aryl halides, but only chloro-
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ACS Catalysis
b was obtained; thus, any uncatalyzed reaction is mini-
Page 2 of 8
2
Table 1. Co(II)-Catalyzed Borylation of chloroanisole,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
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2
2
2
2
2
2
2
3
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5
5
5
5
6
a
2a.
mal (entry 15). Gratifyingly, with a reduced catalyst load-
ing of 2.5 mol % (entry 16), we obtained a comparable
yield of 92 %.
Having identified the optimum conditions with chlo-
roanisole as a standard substrate, we examined the scope
of the present borylation reaction with different aryl chlo-
rides, as depicted in Table 2. Electron-neutral (1a, 15a),
electron-rich (2a-5a) and electron-deficient (6a-9a) aryl
chlorides are converted to corresponding arylboronic
esters in good to excellent yields. Notably, 4-fluorophenyl
boronate (6b) was the sole borylated product from the
reaction of 1-chloro-4-fluorobenzene, leaving the fluoro
group intact. Furthermore, 1,4-dichlorobenzene with 2.5
equiv of B pin /KOMe gave 1,4-diborylated product (9b)
1
entry deviation from standard conditions
H NMR
b
yield (%)
97 (85)
c
1
2
3
4
5
6
7
8
9
none
d
THF instead of MTBE
DME instead of MTBE
toluene instead of MTBE
benzene instead of MTBE
50
76
44
41
63
68
38
0
0
0
81
95
trace
trace
92
d
d
0
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0
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0
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0
d
d
t
KO Bu instead of KOMe
d
d
t
NaO Bu instead of KOMe
LiOMe instead of KOMe
2
2
d
Cs CO instead of KOMe
2
3
in excellent yield. This protocol was also applicable to
substrates having sterically hindered environment around
chloro substituent. Reaction of 2-chlorotoluene (10a)
under standard conditions afforded the corresponding
borylated product in 92% yield. Though, sterically con-
gested 2-chloro-m-xylene 11a, substituted at both ortho
positions, afforded borylation product in only 32% yield.
The system shows excellent chemoselectivity in case of
chlorobenzyl chloride (12a), where the borylation was
d
10
KOAc instead of KOMe
in absence of KOMe
II instead of I
d
1
1
1
1
1
1
1
2
3
4
5
6
III instead of I
CoCl instead of I
2
in absence of I
2.5 mol % of I used
a
Standard conditions: 2a (0.1 mmol), I (5 mol %), KOMe (1.3
equiv), B pin (1.3 equiv), MTBE (0.5 mL) at 50 °C for 8 h (see
Supporting Information (SI) for details). Determined by H
NMR using nitromethane as an internal standard. Isolated
2
2
2
3
b
1
selective for (sp )C-Cl bond, leaving the (sp )C-Cl bond
intact. Substrate having heterocyclic-arene in the system
c
d
(13a) was also tolerable, affording the desired aryl-
yield. Reaction was performed at 70 °C for 20 h.
boronate in 88% yield. In addition, 3-chloropyridine was
transformed to the desired boronate, but in lower yield
Table 2. Substrate Scope of Co(II)-Catalyzed Boryla-
a
tion of Aryl Chlorides.
(14b).
Table 3. Substrate Scope of C0(II)-Catalyzed Boryla-
a
tion of Aryl Halides.
a
Conditions: aryl chloride (1.0 mmol, 1 equiv), I (5 mol %),
B pin (1.3 equiv), KOMe (1.3 equiv), MTBE (5 mL), at 50 °C
for 8 h unless otherwise stated. Isolated yield after chroma-
tographic workup. Yield determined by H NMR using ni-
tromethane as internal standard is given in parentheses.
The reaction was performed at 70 °C. The reaction was
performed using 10 mol % of I, 2.5 equiv of B pin /KOMe for
2
2
1
b
a
c
Conditions: aryl halide (1.0 mmol, 1 equiv), I (2.5 mol %),
B pin (1.3 equiv), KOMe (1.3 equiv), MTBE (5 mL), at 50 °C
2
2
2
2
for 8 h unless otherwise stated. Isolated yield after chroma-
2
0 h.
1
tographic workup. Yield determined by H NMR using ni-
17b
b
2
-ylidene) supported Co-complex (Co(ICy) Cl , II) gave
tromethane as internal standard are given in parentheses.
2
2
c
slightly lower yield than I (entry 12). The Co(IMes) Br
The reaction was performed using 5 mol % of I at 70 °C. The
2
2
1
7c
d
complex (III) displayed comparable reactivity to I (en-
try 13). Ligand is essential for this catalytic process; no
borylated product was observed when the ligand was
omitted (entry 14). In the absence of a Co(II) source, no
reaction was performed using 1.0 equiv of B pin and KOMe.
2 2
e
4-chlorophenyl boronate (22b) was obtained. The reaction
was performed using 10 mol % of I, 2.5 equiv of B pin /KOMe
2
2
f
at 70 °C for 20 h. 1,4-bis(Bpin)benzene was obtained.
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The reaction conditions optimized for aryl chlorides
that IV is the active catalyst in catalytic cycle, EPR exper-
iments were performed (see SI). The EPR active IV could
be produced by the reaction of I with the preformed dibo-
ron ate complex, but not with diboron itself (see SI for
details). A similar EPR signal was observed for the pure IV
as well as for the borylation reaction mixture. These re-
sults further supports that Co(I) species is involved as an
active catalyst in this borylation process.
1
2
3
4
5
6
7
8
9
were found to be compatible with both aryl bromides and
iodides, and they even need less catalyst loading of 2.5
mol % (Table 3). Bromobenzene (16a) gave the desired
boronate ester in 95 % yield. Aryl bromides with electron
donating (17a-19a) and withdrawing (20a-22a) substitu-
ents were borylated in moderate to high yield. Reaction of
1-bromo-4-chlorobenzene (22a) with 1.3 equiv of
B pin /KOMe gave mixture of mono and diborylated
2
2
Based on the experimental results and related reports
products, in ca. 80:20 ratio. To achieve chemoselective C-
Br bond activation over C-Cl bond, reaction was per-
18
on Co-catalyzed borylation reactions, a possible mecha-
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0
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nism for this C-X activation is depicted in Figure 1. The
formed using 1.0 equiv of B pin /KOMe, yielded solely
2
2
active catalyst IV generated from the reduction of I by
monoborylated product (4-chlorophenyl boronate), veri-
+
¯
1
K [B
pin
2
2
OMe] (generated via reaction between B
pin
2
2
fied by H NMR spectroscopy and GC-MS analysis. Using
11f
and KOMe), which undergo ligand exchange reaction
2
.5 equiv of B pin /KOMe at elevated temperature (70 ºC)
2 2
with KOMe to produce
a
cobalt-OMe complex
and longer reaction time (20 h) gave exclusively 1,4-
bis(Bpin)benzene in good yield. To study the steric effect
of substituents, we investigated the borylation of 2-
bromo-1,3-dimethylbenzene (23a), which gave moderate
yield of arylboronate. 4-Bromo-3-methylaniline (24a) gave
the desired product in 49% yield. Biaryl system (25a)
worked well to afford excellent yield of arylboronic ester.
A variety of heteroaryl bromides, such as thiophene, pyri-
dine, quinoline and indole systems (26a-29a) produced
the corresponding boronate esters in moderate to high
yield. Furthermore, aryl iodides (30a and 31a) produced
good yields of the corresponding arylboronic esters. The
method enables convenient gram scale synthesis (6
mmol) with the same efficiency, as demonstrated for 2a
A. Reaction of A with B pin may produce Co-boryl inter-
2
2
mediate B together with formation of MeO-Bpin. Oxida-
tive addition of aryl halide to B followed by reductive
elimination gives the product Ar-Bpin and regenerates
the Co(I) active species IV.
(2b: 1.07 g, 75%), 7a (7b: 1.15 g, 70 %), 15a (15b: 1.3 g, 84 %)
and 19a (19b: 1.16 g, 78 %).
To gain insight into the mechanism, first we conducted
the reactions in the presence of radical scavenger. When
the reaction of 2a with B pin was performed in the pres-
Figure 1. A plausible mechanism of Co-catalyzed boryla-
tion of aryl halides with B pin .
2
2
2
2
CONCLUSIONS
ence of radical scavenger 9,10-dihydroanthracene (1.3
equiv), the borylation product was obtained without any
significant decrease in the yield (85%), indicating that the
borylation does not appear to be a radical process (see SI
for details). In addition, no detected amount of expected
borylated as well as radical cyclization product was ob-
served by NMR and GC-MS analysis, when a radical-clock
experiment was performed using 1-(allyloxy)-2-
iodoobenzene as a substrate under the standard reaction
conditions.
In summary, we have demonstrated an efficient Co-
catalyzed borylation of aryl halides, including aryl chlo-
rides with B pin . The reaction proceeds under mild con-
2
2
ditions, displays broad scope and functional group toler-
ance, and furnishes arylboranates in good to excellent
yields. From a mechanistic standpoint, based on prelimi-
nary experimental results it show that the catalytic cycle
operates via a Co(I)−Co(III) redox couple. Current inves-
tigations are aimed to explore the reactivity of NHC sup-
ported cobalt systems toward more diverse set of sub-
strates.
Given the propensity of cobalt complexes to undergo
redox reaction via Co(I)-Co(III) catalytic cycle, as ob-
2
18
served in Co-catalysed (sp )C–H functionalization, we
speculated that this borylation reaction might have in-
volvement of Co(I) species as the active catalyst. Thus,
ASSOCIATED CONTENT
1
9
AUTHOR INFORMATION
Corresponding Author
adopting
a
modified procedure,
we synthesized
Co(IMes) Cl (IV) by the reaction of Co(IMes) Cl (I) using
2
2
2
Mg dust as a reducing agent. To our delight, using IV as a
catalyst also produced 92% of the borylated product from
*
E-mail: geetharani@iisc.ac.in
2a under standard conditions. The involvement of Co(I)
Notes
The authors declare no competing financial interest.
complex in this borylation process was further confirmed
by a series of NMR monitoring experiments. Treatment of
equimolar amount of I with KOMe and B pin in C D
Supporting Information
2
2
6
6
1
shows the formation of IV, determined by H NMR spec-
1
9
troscopy (δ = 107.27 ppm). To provide further evidence
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Page 4 of 8
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Experimental and spectroscopic data, copies of H, C and B
NMR spectra. This material is available free of charge via the
Internet at http://pubs.acs.org.
From Structural Curiosity to Synthetic Workhorse. Chem. Rev.
2016, 116, 9091-9161.
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(
4) (a) Ishiyama, T.; Miyaura, N. Metal-Catalyzed Reactions of
Diborons for Synthesis of Organoboron Compounds. Chem. Rec.
004, 3, 271-280. (b) Chow, W. K.; Yuen, O. Y.; Choy, P. Y.; So, C.
2
ACKNOWLEDGMENT
M.; Lau, C. P.; Wong, W. T.; Kwong, F. Y. A Decade Advance-
ment of Transition Metal-Catalyzed Borylation of Aryl Halides
and Sulfonates. RSC Adv. 2013, 3, 12518-12539. (c) Murata, M.
Transition-Metal-Catalyzed Borylation of Organic Halides with
Hydroboranes. Heterocycles 2012, 85, 1795-1819. (d) Kubota, K.;
Iwamoto, H.; Ito, H. Formal Nucleophilic Borylation and Boryla-
tive Cyclization of Organic Halides. Org. Biomol. Chem. 2017, 15,
K.G. thanks AllyChem Co. Ltd., China for a gift of B pin , and
the SERB (EMR/2016/000367) and Indian Institute of Science
IISc) start-up research grant, for funding. P.K.V. thanks IISc
Bangalore for a research fellowship. S.M. thanks Kishore
Vaigyanik Protsahan Yojana (KVPY) for fellowship. We also
thank Prof. S. Ramakrishnan, IISc Bangalore for the GC-MS
analysis and Prof. S. Maheswaran, IIT Bombay for his help in
obtaining the EPR Spectra.
2
2
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85-300.
(
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Haloarenes: A Direct Procedure for Arylboronic Esters. J. Org.
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