Synthesis ofortho-arylated and alkenylated benzamides by palladium-catalyzed denitrogenative cross-coupling reactions of 1,2,3-benzotriazin-4(3H)-ones with organoboronic acids

Article abstract of DOI:10.1039/d1nj03706d

An efficient palladium-catalyzed denitrogenative Suzuki-Miyaura type cross-coupling of 1,2,3-benzotriazin-4(3H)-ones with organoboronic acid is described. The reaction is compatible with various aryl and alkenyl boronic acids affordingortho-arylated and alkenylated benzamides in good to high yields. Heteroaromatic boronic acids were also successfully employed. Along with this, a coupling reaction was established by using phenyl boronate ester as the coupling partner. The reaction is believed to proceedviaa five-membered aza-palladacyclic intermediate. DFT calculations were studied comparing the reactivity of palladium and nickel complexes in the five-membered aza-metallacycle formation from 1,2,3-benzotriazin-4(3H)-ones. The application of the reaction was successfully demonstrated by convertingortho-alkenylated products toortho-alkylated products in high yieldsviaa reduction reaction.

Full text of DOI:10.1039/d1nj03706d

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Synthesis of ortho-arylated and alkenylated
benzamides by palladium-catalyzed
Cite this: DOI: 10.1039/d1nj03706d
denitrogenative cross-coupling reactions of
1,2,3-benzotriazin-4(3H)-ones with organoboronic
acids†
a
b
a
Madasamy Hari Balakrishnan, Madasamy Kanagaraj, Velayudham Sankar,
b
b
Mahesh Kumar Ravva
and Subramaniyan Mannathan
*
An efficient palladium-catalyzed denitrogenative Suzuki–Miyaura type cross-coupling of 1,2,3-benzotriazin-
(3H)-ones with organoboronic acid is described. The reaction is compatible with various aryl and alkenyl
4
boronic acids affording ortho-arylated and alkenylated benzamides in good to high yields. Heteroaromatic
boronic acids were also successfully employed. Along with this, a coupling reaction was established by using
phenyl boronate ester as the coupling partner. The reaction is believed to proceed via a five-membered
aza-palladacyclic intermediate. DFT calculations were studied comparing the reactivity of palladium and
nickel complexes in the five-membered aza-metallacycle formation from 1,2,3-benzotriazin-4(3H)-ones.
The application of the reaction was successfully demonstrated by converting ortho-alkenylated products to
ortho-alkylated products in high yields via a reduction reaction.
Received 2nd August 2021,
Accepted 12th August 2021
DOI: 10.1039/d1nj03706d
rsc.li/njc
7
–9
successfully demonstrated by employing carbon–oxygen
and
Introduction
10
carbon–nitrogen compounds as the electrophilic counterparts.
A transition-metal catalyzed cross-coupling reaction remains one of Despite being effective, formation of a stoichiometric amount of
11
the robust protocols to construct carbon–carbon and carbon-hetero (pseudo) halides as waste during the reaction is inevitable. There-
1
bonds in organic synthesis. In particular, palladium-catalyzed fore, the development of newer, more efficient methodologies for
cross-coupling reactions have played a vital role in the preparation the synthesis of biaryls with minimum waste generation is still in
of molecules having potential applications in the areas of pharma- high demand.
2
ceuticals, agriculture, agrochemicals, and so on. A variety of
Significant efforts have been devoted towards the synthesis of
palladium-catalyzed reactions, including Heck coupling, cross- biaryls in a step and atom economical fashion. Representative
coupling (Kumada, Stille, Negishi, Suzuki–Miyaura, Hiyama), examples include transition-metal catalyzed C–H bond functionali-
1
2
13
Tsuji–Trost allylation, and Buchwald–Hartwig amination reactions zation reactions, and metal-catalysed decarboxylative, decar-
3,4
14
10
have been well established. Of these cross-coupling reactions, the bonylative, and denitrogenative cross-coupling reactions. In this
Suzuki–Miyaura reaction between aryl boronic acids and aryl halides context, the transition metal-catalyzed denitrogenative arylation
is, arguably, one of the most efficient transformations for the reaction of 1,2,3-triazoles has emerged as an attractive strategy for
synthesis of biaryl molecules in organic synthesis. This methodol- the synthesis of biaryls. Mechanistically, the reaction proceeds via
ogy has numerous advantages, including mild reaction conditions, a metallocarbene or five-membered metallacycle intermediate with
good functional group compatibility, low toxicity of the organoboron the extrusion of an environmentally friendly molecular nitrogen as a
5
15
15
compounds, and commercial availability of many aryl boronic by-product. Even though a variety of metal-catalyzed denitrogena-
acids. The significance of this cross-coupling reaction was also tive transannulations of 1,2,3-triazoles has been well established,
6
16
only a few reports are available in the literature employing them as
the electrophilic counterpart for the biaryl synthesis (Fig. 1). In 2017,
Tang et al. reported a palladium-catalyzed denitrogenative Suzuki
and carbonylative Suzuki coupling reaction of benzotriazoles
with organoboronic acids to prepare structurally diverse ortho-
a
b
Department of Chemistry, SRM Institute of Science and Technology,
Kattankulathur, Chennai, 603203, India
Department of Chemistry SRM University, AP, Andhra Pradesh 522502, India.
E-mail: mannathan.s@srmap.edu.in
15a
amino-substituted biaryl and biaryl ketone derivatives.
Re-
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
15b
15c
d1nj03706d
cently, our group and Cheng et al. independently reported
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a
Table 1 Optimization studies
b
Entry
1
Ligand
Solvent
Additive
Yield (%)
c
Xantphos
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Toluene
THF
DMF
DMF
DMF
DMF
DMF
DMF
Na
2
Na
2
Na
2
Na
2
Na
2
Na
2
Na
2
Na
2
Na
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
95 (93)
d
g
3
2
PPh
35
20
21
15
17
g
3
4
5
6
7
8
9
dppm
dppe
g
g
dppp
g
TFP
e
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
—
51
41
11
83
53
41
—
—
90
Fig. 1 Palladium-catalyzed denitrogenative arylation reactions of 1,2,3-
triazoles.
1
1
1
1
0
1
2
3
2 3
K CO
NaOAc
—
f
Na
2
Na
2
Na
2
CO
CO
CO
3
3
3
a nickel-catalyzed denitrogenative cross-coupling reaction between 14
h
15
Xantphos
1
,2,3-benzotriazin-4(3H)-ones and organoboronic acids to prepare
a
ortho-arylated and alkenylated benzamides.
We have been interested in the metal-catalyzed denitrogenative
cross-coupling reaction of 1,2,3-triazoles, particularly involving
Unless otherwise mentioned, all reactions were carried out using 1a
(10 mol%), ligand (10 mol%),
(0.10 mmol), solvent (2.0 mL), 100 1C, 12 h under argon
(0.10 mmol), 2a (0.15 mmol), Pd(OAc)
2
2 3
Na CO
b
c
d
atmosphere. GC yields. Isolated yield. 20 mol% of ligand has
e
f
1
,2,3-benzotriazinones as the electrophilic counterpart. In this used. Reaction was carried out at 50 1C. Reaction was carried out
g
without palladium acetate. dppm
dppe = bis(diphenylphosphino)ethane; dppp = bis(diphenylphosphino)
propane, TFP = Tri(2-furyl)phosphine. The reaction was carried out with
= bis(diphenylphosphino)methane;
context, we have recently described a denitrogenative alkylidena-
tion and ortho-alkynylation of 1,2,3-benzotriazinones by using a
palladium/copper catalyst. Literature reports reveal that the 3.0 equivalent of water.
h
17
generation of the aza-palladacycle intermediate from 1,2,
3
-benzotriazinones using a palladium catalyst is relatively
used, or the reaction was performed at a lower temperature
entry 7). The solvent used played a vital role in obtaining 3aa in
unknown compared to nickel-catalyzed denitrogenative transan-
nulation and coupling reactions.
(
17,18
Considering the versatility of
high yield. Among the solvents that we screened, DMF
appeared to be the best, affording the desired product in 93%
yield, whereas other solvents, such as toluene and THF, pro-
vided 3aa in 41% and 11% yields respectively (entries 8 and 9).
Other palladium precursors, including PdCl (PPh ) and
a palladium catalyst in Suzuki–Miyaura reactions and the impor-
tance of 1,2,3-benzotriazinones as the electrophilic counterpart,
we are delighted to perform a denitrogenative cross-coupling
reaction of 1,2,3-benzotriazin-4(3H)-ones and organoboronic acids
to prepare biaryl motifs. Herein, we disclose the first palladium-
catalyzed direct Suzuki–Miyaura type cross-coupling of 1,2,
2
3 2
2
Pd(TFA) , were also effective, furnishing the desired product
in 81% and 90% yields, respectively (see the ESI†). The effect of
water on the present reaction conditions was examined (see the
ESI†) and we found that the reaction can tolerate 2 equivalents
of water without a significant drop in the product yield. However,
the presence of an excess amount of water (42.0 equiv.) during the
reaction led to the formation of N-(4-methoxyphenyl)benzamide as
the by-product and decreased the desired product yield (entry 15).
Having the optimized reaction conditions in hand, we
3-benzotriazinones with aryl boronic acids for the synthesis of
valuable biaryl motifs. It is well known that biaryls and hetero-
biaryls are essential motifs present in pharmaceuticals, natural
products, and organic materials.
19
Results and discussion
Treatment of 1,2,3-benzotriazin-4(3H)-ones (1a) and phenyl- studied the scope of the ortho-arylation reaction with different
boronic acid (2a) with 10 mol% of Pd(OAc) , 10 mol% of organoboronic acids (Scheme 1). The reaction of 1a with
xantphos, and 1.0 equiv. of sodium carbonate in DMF at electron-rich boronic acids 2b and 2c gave the arylated products
2
100 1C for 12 hours afforded the desired ortho-arylated product 3ab and 3ac in 78% and 81% yields, respectively. Similarly, aryl
3aa in 93% isolated yield (Table 1, entry 1). Control experiments boronic acids (2d–h) possessing electron-withdrawing groups
revealed that no desired product was formed in the absence of like –F, –CF , –CN, –CHO, and –COCH in the para position of
3 3
either palladium or xantphos (entries 13 and 14). Switching the the phenyl ring furnished the corresponding products 3ad–3ah
ligand from xantphos to other phosphine ligands, such as in slightly higher 88% to 95% yields. These results are in
PPh , tri(2-furyl)phosphine (TFP), dppe, and dppp, led to 3aa contrast with our earlier reported nickel catalyst system, where
3
only in low yield (entries 2–6). Moreover, the reaction yield the electron-donating group substituted aryl boronic acids
1
5b
decreased significantly when other additives, such as potas- afforded better yields than electron-withdrawing ones.
The
sium carbonate (entry 10) and sodium acetate (entry 11), were coupling of 3-substituted-phenylboronic acids, 2i and 2j, with
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Scheme 2 Scope of 1,2,3-benzotriazinones. Reaction conditions:
1
(0.40 mmol), 2a (0.60 mmol), Pd(OAc)
2
(10 mol%), Xantphos
(
10 mol%), Na CO (1.0 equiv.) in dry DMF (2.0 mL), 100 1C, 12 h. Isolated
2
3
yields.
Scheme 1 Scope of organoboronic acids. Reaction conditions: 1a
(
0.40 mmol), 2 (0.60 mmol), Pd(OAc)
2
(10 mol%), Xantphos (10 mol%),
Na CO (1.0 equiv.) in dry DMF (2.0 mL), 100 1C, 12 h. Isolated yields.
2
3
1a furnished products 3ai and 3aj in 73% and 81% yields
respectively. Pleasingly, heteroaryl boronic acids, such as thio-
phene boronic acid (2k) and benzofuranboronic acid (2l),
successfully participated in the reaction and afforded the
products 3ak and 3al in 84% and 73% respectively. To our
delight, alkenyl boronic acids, such as styryl boronic acid (2m)
Scheme 3 Arylation reaction of 1a with phenylboronate ester (4).
and its derivatives 2n and 2o, afforded the ortho-alkenylated catalyst in glacial acetic acid at room temperature gave ortho-
products 3am–3ao in 61% to 71% yields. Satisfyingly, alkylated benzamides 5a and 5b in high yields (Scheme 4).
n-pentenyl boronic acid (2p) also provided 3ap in 82% yield. A gram scale reaction of 1a and 2a was also demonstrated using
It is noteworthy to mention that alkyl boronic acid failed to 5 mol% of Pd(OAc) to prepare ortho-arylated benzamide 3aa in
2
participate in the reaction.
89% yield.
A plausible mechanism for the present catalytic reaction
The scope of 1,2,3-benzotriazin-4(3H)-ones with 2a is shown
in Scheme 2. In general, 1,2,3-benzotriazin-4(3H)-ones having is shown in Scheme 5, based on the reported metal-catalyzed
N-aryl substituents participated successfully and gave the ortho- denitrogenative reaction of 1,2,3-benzotriazin-4(3H)-ones.
arylated products 3ba–3ha in good to high yields (65% to 92%). The reaction proceeds via oxidative addition of Pd(0) to 1,
On the other hand, reactions involving 1,2,3-benzotriazin- 2,3-benzotriazin-4(3H)-ones affording a five-membered aza-
4(3H)-ones bearing N-alkyl substituents were unsuccessful. palladacyclic intermediate and followed by transmetallation
The present catalytic reaction exhibited good tolerance of the
functional groups–like methyl, fluoro, methoxy, morpholine,
and ester–on the backbone aromatic ring of 1,2,3-benzotriazin-
3(H)-one and furnished the expected products 3ia–3ma in 62%
to 81% yields. To our delight, phenyl boronate ester 4 success-
fully participated in this reaction with 1a and afforded 3aa in
89% yield (Scheme 3).
To overcome the incompatibility of alkylboronic acid in the
present catalytic reaction, a reduction reaction of ortho-
alkenylated benzamide was performed. Thus, the reaction of
3
am and 3ap in the hydrogen atmosphere using Pd/C as the Scheme 4 Synthesis of ortho-alkylated benzamides 5.
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cleavage of a C–N bond and formation of a M–C (M = Ni and Pd)
bond via the second transition state to give the five-membered
complex M–Ph3 (M = Ni and Pd). The calculated activation
À1
energy barriers for Ni and Pd complexes are 16 kcal mol and
À1
3
2 kcal mol respectively. These results reveal that the metal
insertion reaction to form a five-membered aza-metallacycle
intermediate using a palladium complex is indeed possible.
Meanwhile, the high energy barriers for transition states
Pd-TS1 and Pd-TS2 justify the requirement of a higher reaction
temperature for the palladium-catalyzed reaction in the deni-
trogenative reactions of 1,2,3-benzotriazinones. The overall free
energies of Ni-based and Pd-based reactions are more or less
the same. The optimized geometries of reactants, transition
states, intermediates, and products are shown in the ESI.†
Scheme 5 Proposed mechanism.
Conclusions
of phenylboronic acid with 6 to give 7. Reductive elimination of
In conclusion, we have successfully described the first denitro-
genative cross-coupling reaction of 1,2,3-benzotriazin-4(3H)-
ones with organoboronic acids using palladium as the catalyst.
The reaction is compatible with various aryl and alkenyl
boronic acids affording ortho-arylated and alkenylated benza-
mides in good to high yields. Together with our previous
7
affords the desired product 3aa and regenerates the Pd(0) for
the further catalytic cycle.
A literature survey on metal-catalyzed denitrogenative reac-
tions of 1,2,3-benzotriazin-4(3H)-ones discloses that nickel
complexes are the frequently employed catalyst system. Con-
versely, only a few reports are available in the literature with
palladium as the catalyst. To understand the reactivity of nickel
and palladium complexes in the denitrogenative reactions of
1
6
1
5b
report,
the present catalytic system is successful for the
carbonyls and cyanide substituted aryl boronic acids. DFT
calculations were performed, for the first time, comparing the
reactivity of palladium and nickel complexes in the five-
membered aza-metallacycle formation from 1,2,3-benzotriazin-
1
,2,3-benzotriazinones, density functional theory-based calcu-
lations were performed on the extrusion of a N molecule and
3 2
metal insertion reactions using Ni–(PMe and Pd–(PMe )
2
3
)
2
4(3H)-ones. A detailed mechanistic study of the arylation reaction
complexes. The energy barriers and free energies of these two
reactions are compared and shown in Fig. 2.
As shown in Fig. 2, the first step involves the formation of a
seven-membered ring (Ni–Ph2 and Pd–Ph2) intermediate via a
is under way in our laboratory. Overall, the present catalytic
system could serve as an excellent complement and alternative
to the Suzuki–Miyaura cross-coupling reaction to synthesize ortho-
arylated biaryls.
3 2
transition state. In the case of the Ni–(PMe ) based complex,
we have observed significantly less activation energy barrier
À1
(
B0.2 kcal mol ), whereas in the case of Pd–(PMe
3
)
2
, the same
À1
Conflicts of interest
value increased to 12.55 kcal mol . The next step involves the
There are no conflicts to declare.
Acknowledgements
We thank the Department of Science and Technology (DST),
New Delhi, India (DST/INSPIRE/04/2015/002987), for support of
this research under a DST-INSPIRE faculty scheme. We also
extend our sincere thanks to Prof. M. Sasidharan, SRM Institute
of Science and Technology, Chennai, for providing laboratory
facilities.
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