RhIII-Catalyzed Straightforward Synthesis of Benzophenanthroline and Benzophenanthrolinone Derivatives using Anthranils

Article abstract of DOI:10.1002/chem.201806373

An efficient pot-economic and step-economic Rh^III-catalyzed site-selective direct amination/annulation strategy was developed for the synthesis of benzophenanthroline derivatives using quinoline N-oxides and anthranils. The method was further extended to the synthesis of nitrogen-containing extended π-conjugated benzophenanthrolinone derivatives. Late-stage functionalizations of cinchonidine and cinchophen derivatives and synthesis of a bioactive quinolino-indole were achieved.

Full text of DOI:10.1002/chem.201806373

A Journal of
Accepted Article
Title: Rh(III)-Catalyzed Straightforward Synthesis of
Benzophenanthroline and Benzophenanthrolinone Derivatives
using Anthranils
Authors: Aniruddha Biswas, Souradip Sarkar, and Rajarshi Samanta
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To be cited as: Chem. Eur. J. 10.1002/chem.201806373
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10.1002/chem.201806373
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Rh(III)-Catalyzed Straightforward Synthesis of
Benzophenanthroline and Benzophenanthrolinone Derivatives
using Anthranils
Aniruddha Biswas, Souradip Sarkar and Rajarshi Samanta*[a]
Abstract: An efficient pot-economic and step-economic Rh(III)-
catalyzed site-selective direct amination/annulation strategy was
developed for the synthesis of benzophenanthroline derivatives
using quinoline N-oxides and anthranils. The method was further
extended to the synthesis of nitrogen-containing extended π-
multistep procedures and suffer from poor yields or poor
functional group tolerance.[2e-2g,4] Arguably, site-selective C-H
functionalization/annulation is one of the best methods to access
N-doped PAHs in
a straightforward, facile and efficient
manner.[5,6] Retrosynthetically, direct C8-aryl amination of
quinoline derivative followed by condensation or oxidative
coupling can provide the desired N-PAHs. Direct site-selective
C-H bond functionalizations of quinoline are recent subject of
interest.[7] Especially, a significant progress has been made on
direct introduction of various functional groups at its C8 position
by others[8] and us[9]. In pioneering work, Chang’s group
elegantly established C8-amidation of quinoline N-oxides under
Ir(III)[10] and Rh(III)[11] catalysis using various amidating sources.
Loh and co-workers also established an Rh(III)-catalyzed
alternative strategy for the C8-amidation of quinoline N-oxide
using amidobenziodoxolone as the coupling partner.[12] Very
recently, Cui’s group described another Rh(III)-catalyzed C8-
amidation of quinoline N-oxide using commercially available
trifluoroacetamide.[13] Recently, benzo[c]isoxazoles (anthranils)
were highly admired as a bifunctional arylaminating agent under
conjugated
benzophenanthrolinone
derivatives.
Late-stage
functionalizations of cinchonidine and cinchophen derivatives and
synthesis of a bioactive quinolino-indole were furnished.
In contemporary organic synthesis, efficiency and environmental
sustainability are the key factors. To address these issues,
effective approaches like “step-economic” and “pot-economic”
synthesis has emerged rapidly due to its simplicity and
applicability in minimizing waste and reaction time.[1] Among
nitrogen-containing
polyaromatic
hydrocarbons
(PAHs),
[1,10]phenanthroline and [1,10]phenanthrolin-one are frequent
motifs in many pharmaceuticals, natural products, organic
materials and ligands for catalysis (Figure 1).[2,3] Especially,
these scaffolds are used as potential ligands in gold catalysed
transformations.[3m-3o]
redox-neutral conditions for the direct aryl amination of sp2 and
15]
sp3 C-H bonds[14,
PAHs.[16-19]
and straightforward construction of N-
C-8 amidation of quinoline N-oxides
Rh(III)
i) Chang group: Ir(III); TsN3 or
1,4,2-dioxazol-5-one
Rh(III); CBZNHCl
ii) Loh group: Rh(III);
amidobenziodoxolone
iii) Cui group: Rh(III); CF3CONH2
amidating
N
N
O
agents
NH
H
O
R
Synthesis of N-Doped PAHs using anthranils:
O
N
(a)
(b)
(d)
Bn
HN
N
COAr
FA
N
Au(III)
N
T
III),
Rh(
R
Hashmi
group
PG
Li group
DG
O
e
Rh(III)
PivOH
N
Py
N
Rh(
III)
(c)
Figure 1: Important benzo[1,10]phenanthroline and benzo[1,10]phenanthrolin-
one scaffolds
N
N
r
le o
ndo
zai
7-a
dol
y-in
N-P
X
CH=
Ph
X =
NTs
O,
Wang group
& Li group
Kim group
(e) Present work
O
However, reported methods for their synthesis are in-general
i) Rh(III)
i) Rh(III)
H
N
O
H
ii) TFA, PCl3
"one-pot"
ii) Zn iii) TBHP
N
N
N
[a]
A. Biswas, S. Sarkar and Dr. R. Samanta
Department of Chemistry
O
H
N
N
Indian Institute of Technology Kharagpur
Kharagpur 721302, India
E-mail: rsamanta@chem.iitkgp.ac.in
Scheme 1. Direct amination/annulation strategies for N-containing extended
π-conjugated systems.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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In a recent report, Hashmi and co-workers elegantly studied
Au(III)-catalyzed construction of 2-amino pyrroles and quinoline-
based polyazaheterocycles (Scheme 1a).[16a] In interesting
provided the monoarylaminated/annulated product 5l selectively
in good yield.
developments,
Li’s
group
described
Rh(III)-Catalyzed
R1
[Cp*RhCl2]2 (2 mol%),
AgNTf2 (10 mol%),
NaOAc (50 mol%), DCE
R1
R2
amination/annulation of arenes/heteroarenes using anthranils
(Scheme 1b & c).[17] Wang’s group independently revealed a
tandem Rh(III)-catalyzed amination/annulation strategy to
synthesize indoloquinoline derivatives (Scheme 1c).[18] Kim’s
group also extensively studied Rh(III)-catalyzed synthesis of
acridine derivatives using various coupling partners (Scheme
1d).[19] However, as per best of our knowledge, there is no report
R2
O
N
N
O
N
followed by TFA & PCl3
N
1
5
2
N
N
N
N
N
N
N
N
80%, 5b
75%, 5c
69%, 5d
78% (61%)[a], 5a
for
the
synthesis
of
benzophenanthroline
and
Ph
OMe
Ph
benzophenanthrolin-one class of N-doped PAHs using pot and
step-economic efficient strategy. Intrigued by our latest studies
on step-economic synthesis of N-containing extended π-
conjugated systems[9][20], we envisioned that similar idea might
help us to obtain our desired N-containing extended π-
conjugated systems. Herein, we report Rh(III)-catalyzed site-
selective direct strategies for the pot-economic construction of
N
N
N
N
N
N
74%, 5e
N
66%, 5g
72%, 5f
81%, 5h
N
CF3
Br
N
N
N
N
N
81%, 5i
N
N
72%, 5j
67%, 5l
N
49%, 5k
Ph
benzophenanthroline
and
step-economic
synthesis
of
benzophenanthrolin-one (Scheme 1e).
MeO
MeO
Our investigation started with the reaction of quinoline N-oxide
(1a) with anthranil (2a) under different catalytic conditions.
During the initial screening of suitable transition metal catalyst,
[Cp*RhCl2]2 was found out to be the best one in presence of
AgNTf2 additive surpassing the other known transition metal
catalysts like [Ru(p-cymene)Cl2]2, [Cp*IrCl2]2, [Cp*Co(CO)I2] with
46% isolated yield of 3a (see ESI table 1, entries 1-4). For
further improvement of the yield of 3a, various acetate additives
were tested. With our great pleasure, NaOAc was found to be
the best one (see ESI table 1, entries 5-9) in DCE solvent with
89% isolated yield of 3a. Other solvents did not turn out be
effective except THF with 74% yield of 3a (see ESI table 1,
entries 10-14). As the aryl amination reaction didn’t proceed with
satisfactory yield in the presence of an acid additive (important
for annulations), we planned for sequential addition of required
reagents in one pot strategy for the synthesis of our desired
benzo[b][1,10]phenanthroline (5a). To optimize the yield of
annulated product 5a in the same reaction system, we added
TFA followed by PCl3 (see ESI table 1, entries 15-18) with 71%
of isolated yield. More simply, both TFA (8 equiv) and PCl3 (4
equiv) were added together after complete formation of 3a and
reaction was continued for 12 h. Gladly, the isolated yield of the
desired product 5a was found to be best with 78% (see ESI
table 1, entry 19) while the yield of 5a got decreased under less
reaction time (see ESI table 1, entry 20).
N
MeO
N
N
N
N
71% 5o[c]
76%, 5n[c]
N
71%, 5m[b]
Ph
Cl
X= F; 65%, 5q
= Cl; 73%, 5r
= Br; 58%, 5s
X
O
O
N
N
N
N
81%, 5t
73%, 5p[b]
N
N
Scheme
2.
Scope
of
benzophenanthroline
via
direct
C8-
arylamination/annulation strategy. Reaction Conditions: 1 (0.2 mmol), 2 (0.4
mmol), [RhCp*Cl2]2 (2 mol%), AgNTf2 (10 mol%), NaOAc (50 mol%), DCE (0.2
M), 18-24 h, 110 °C, Then TFA (8 equiv) and PCl3 (4 equiv), 6-8 h 110 °C; [a]
reaction was done in 2 mmol scale; [b] Reaction temperature: 150 °C; [c]
NaOAc (1 equiv) used.
Additionally, the structure of 5b and 5l were unequivocally
confirmed via the comparison of known literature data.[2g, 4a] Next,
the scope with different anthranil derivatives was explored.
Pleasingly, anthranils with different electronic and steric
properties provided the desired benzophenanthroline derivatives
with good to excellent yields (Scheme 2, 5m-5t).
Our preliminary investigations focused on the synthesis of
benzophenanthroline derivatives having electronically and
sterically variable functional groups. Initially, different quinoline
N-oxides were surveyed (Scheme 2, 5a-5l). Alkyl groups and
electron donating methoxy group were well tolerated during the
operation (Scheme 2, 5a-5f). Interestingly, a promising scope
with more extended conjugated systems also synthesized in
very good yields (Scheme 2, 5g-5i). Next, the halogen also
firmly accommodated under the optimized conditions keeping
the window open for further modifications (Scheme 2, 5j). Scope
with electron withdrawing CF3 group also generated albeit in
moderate yield (Scheme 2, 5k). Gratifyingly, another important
class of N-containing heterocycle, that is, acridine N-oxide also
standard
N
N
conditions
2a
N
OBn
OBn
N
N
O
cinchonidine N-oxide
67%, 5u
1u
CO2Me
standard
conditions
CO2Me
N
N
2a
N
Ph
68%, 5v
cinchophen N-oxide
1v
O
Ph
Scheme 3. Late-stage modification of cinchonidine and cinchophen derivative
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Further, to demonstrate the application of the developed method
late-stage modifications were carried out on more complex
bioactive molecules. Notably, cinchonidine N-oxide substrate
was modified to its benzophenanthroline derivative in 67% yield
under the developed reaction conditions (Scheme 3, 5u). This
compound can be an important strategic platform to generate
useful bifunctional catalysts. The method was further extended
towards the modification of another drug molecule cinchophen
derivative in good yield under the optimized conditions (Scheme
3, 5v).
also provided the monoarylaminated/oxidatively coupled
derivative 6i in good yield. Various anthranils were also explored
for the construction of benzophenanthrolinone core (6j-6l).
O
R2
R1
i) [Cp*RhCl2]2 (2 mol%),
AgNTf2 (10 mol%),
NaOAc (50 mol%), DCE
R1
R2
O
N
N
O
N
H
ii) Zn; iii) TBHP
6
2
1
N
O
O
O
O
OMe
Scheme 5. Step-economic synthesis of an advanced intermediate of the
potent drug candidate. Reaction conditions: i) 1 (0.2 mmol), 2 (0.4 mmol),
[RhCp*Cl2]2 (2 mol %), AgNTf2 (10 mol%), NaOAc (50 mol%), DCE (0.2 M), 18
h, 110 °C; ii) Zn dust (7 equiv), THF: aq. NH4Cl (1:1, 5 mL), 10 min, rt. iii) 4a
(0.1 mmol), BF3.Et2O (0.12 mmol), N2=CHCO2Me (0.5 mmol), DCM, 0 °C-rt, 2
h.
N
N
H
N
N
H
H
H
N
N
N
N
74%, 6d
(Fluorescent probe:
DNA detection)
59%, 6c
48%, 6b
73%, 6a
O
O
O
Br
To delineate another practical utility of the developed protocol, a
drug candidate used for NHE related disease was developed
(Scheme 5) under the optimized conditions.[21] First, the crucial
Rh(III)-catalyzed C8-arylamination of quinoline N-oxide (1a)
followed by Zn-mediated deoxygenation was performed to
obtain the 2-aminoaldehyde compound 4a which was further
converted into the known substituted indole derivative 7 via
[1,2]-aryl shift.[22] This advanced precursor 7 can be transformed
into the potent drug candidate by literature known steps.[21]
R'
N
H
N
H
N
H
N
N
N
R' = H, 82%, 6g
77%, 6e
70%, 6f
= CO2Me, 75%, 6h
(cincophen derivative)
Ph
O
O
O
MeO
R''
N
N
NH
N
H
H
N
N
R'' = Br, 66%, 6k
67%, 6i
57%, 6j
= Cl, 71%, 6l
Scheme 4. Scope of benzophenanthrolinone via C8-amination/oxidative
coupling based strategy. Reaction conditions: i) 1 (0.2 mmol), 2 (0.4 mmol),
[RhCp*Cl2]2 (2 mol%), AgNTf2 (10 mol%), NaOAc (50 mol%), DCE (0.2 M), 18-
24 h, 110 °C; ii) 3 (amount obtained from step i), 1:1 THF & 30% aq. NH4Cl
solution (5 mL), Zn dust (7 equiv w.r.t. 1), 10 min, rt; iii) 4 (amount obtained
from step ii), DCE, TBHP in decane (5 equiv w.r.t. 1), 110°C, 6-12 h. Yields
were determined after three steps.
Furthermore, we hypothesized that the developed C8-
arylamination can be forwarded to the construction of important
benzophenanthrolinone[3] core in step-economic fashion. Hence,
the crucial Rh(III)-catalyzed C8-aryl amination of quinoline N-
oxides, followed by zinc-mediated deoxygenation and
subsequent TBHP based oxidative coupling led to the formation
of expected benzophenanthrolinone moiety (Scheme 4). A brief
survey of the substrate scope revealed that the generation of
this N-doped extended π-conjugated core (N-PAHs) via our
strategy is quite general having different substitutions both in N-
oxide as well as in anthranil part. Electron donating alkyl or
methoxy group at the quinoline core survived with very good
yields (Scheme 4, 6a-6e). Next, Compound 6d, known as a
fluorescent probe in DNA detection was synthesized using this
unified strategy.[2h] Further, halogen or electron withdrawing
groups in quinoline moiety also firmly tolerated under the
developed conditions (6f-6h). More conjugated acridine N-oxide
Scheme 6. Control experiments for mechanistic studies
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Numbers of control experiments were carried out to figure out
more insight of the developed protocol (Scheme 6). First,
substituted quinoline N-oxides 1f and 1k were treated with 2a
under optimized conditions to know the electronic preference.
The outcome of the competition experiment shows that the rate
of the reaction favours the electron-rich N-oxide over the
electron-poor one (Scheme 6i). Next, treatment of 1a with
CD3CO2D as the co-solvent in the absence or presence of 2a
afforded significant H/D scrambling at the C8-position (Scheme
6ii) under optimized conditions. These results reveal that C-H
activation step at C8-position is highly reversible and the further
step ahead the C-H metalation is faster. Further, both
competitive and parallel experiments with quinoline N-oxide (1a)
and 8-d1quinoline N-oxide (1a’) were performed to reveal
whether C-H bond metalation is the rate determining step or not
(Scheme 6 iii-iv). The obtained KIE (~1.5) suggests that C-H
bond cleavage might not be involved in the rate determining step.
Based on control experiments and previous literature[14, 15], a
plausible mechanism for this unified Rh(III)-catalyzed
straightforward strategy is proposed for the synthesis of
benzophenanthroline and benzophenanthrolinone derivatives
(Scheme 7).
In conclusion, we have accomplished a one-pot Rh(III)-
catalyzed site-selective direct arylamination/annulation strategy
for the synthesis of benzophenanthroline derivatives using
isoxazoles as coupling partner. The method has been extended
to the step-economic synthesis of benzophenanthrolinone
derivatives and bioactive quinolino indole scaffold. Late-stage
functionalizations of bioactive quinoline scaffolds were carried
out. The application of benzophenanthroline derivatives as an
ligand in catalytic reactions is currently underway in our
laboratory.
Experimental Section
Quinoline N-oxide 1a (29 mg, 0.2 mmol) was dissolved in 1 mL of dry
DCE in a 10 mL sealed tube. Then [Cp*RhCl2]2 (2 mol%, 2.4 mg)
followed by AgNTf2 (10 mol%, 7.8 mg), NaOAc (50 mol% 8.2 mg) and
anthranil (2a, 45.5 mg, 0.4 mmol) were added to the solution. The
reaction mixture was stirred for 18 h at 110 °C. After the mixture was
cooled to room temperature, CF3COOH (121 µL, 8 equiv.) and PCl3 (70
µL, 4 equiv.) were added to the same reaction mixture and stirred for 12
h at 110 °C. After the completion of reaction, the reaction mixture was
cooled to room temperature and diluted with CH2Cl2 (10 mL) and
neutralized using saturated NaHCO3 solution. The organic layer was
extracted with CH2Cl2 and dried over anhydrous Na2SO4, and
concentrated under reduced pressure. The residue was purified by flash
column chromatography to obtain the pure products 5a.
Acknowledgements
We thank CSIR, India for financial assistance through EMR
project [02(0323)/17/EMR-II] and fellowship (AB). UGC, India is
acknowledged for fellowship (SS). Authors appreciate DST,
India (SR/FST/CSII-026/2013) for 500 MHz NMR facility and
CRF(IIT Kharagpur) for the analytical facility.
Keywords: C-H Amination/Annulation • Anthranil • Rh(III)-
catalysis • N-PAHs • Step-economic
Scheme 7. Plausible mechanism
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assistated C8-selective C-H bond metalation provides five-
membered rhodacycle B. Further, nucleophilic nitrogen center of
anthranil coordinates with B to afford the intermediate C.
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species delivers intermediate
D which further undergoes
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compound 6a.
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10.1002/chem.201806373
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
Aniruddha Biswas, Souradip Sarkar and
Rajarshi Samanta*
O
RhIII
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RhIII
i)
H
N
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ii) TFA, PCl3
"one-pot"
ii) Zn iii) TBHP
N
N
Page No. – Page No.
Rh(III)-Catalyzed Straightforward
Synthesis of Benzophenanthroline
and Benzophenanthrolinone
Derivatives using Anthranils
N
H
N
O
22 examples
49-81%
12 examples
N
48-82%
Rh(III)-catalyzed site-selective straightforward synthesis of benzophenanthroline
and benzophenanthrolinone derivatives
This article is protected by copyright. All rights reserved.