Rh(iii)-Catalyzed: Ortho -C-(sp2)-H amidation of ketones and aldehydes under synergistic ligand-accelerated catalysis

Article abstract of DOI:10.1039/c8cc07006g

Rh(iii)-Catalyzed ortho-C-H amidation of ketones and aldehydes under cooperative metal organocatalysis has been utilized for synthesizing various ortho-amidocarbonyl analogs, and the reaction for the aldehyde proceeds at ambient temperature. The aniline derivative 3,5-bis(trifluoromethyl)aniline promotes the amidation reaction via a transient imine directing group. The efficient amidation agent is dioxazolone. The synthetic utility has been demonstrated in the synthesis of quindolinone alkaloids.

Full text of DOI:10.1039/c8cc07006g

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Rh(III)-Catalyzed ortho-C-(sp2)-H Amidation of Ketones and Al-
dehydes under Virtue of Synergistic Ligand Accelerated Catalysis†
Received 00th January 20xx,
Accepted 00th January 20xx
Akshay Ekanath Hande, Vinay Bapu Ramesh and Kandikere Ramaiah Prabhu*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A Rh(III)-Catalyzed directed ortho-C-H amidation of ketones and
aldehydes under cooperative metal organocatalysis has been
exploited for synthesizing various ortho-amidocarbonyl analogs,
and the reaction for aldehyde proceeds at ambient temperature.
The aniline derivative, 3,5-bis(trifluoromethyl) aniline , promoted
the amidation reaction via a transient imine directing group. The
efficient amidation agent is dioxazolone. The synthetic utility has
been demonstrated in the synthesis of quindolinone alkaloids.
directing groups including ketone, ester, carboxylic acid,
imine,and amide have accomplished the ortho-C-(sp2)-H
amination using transition metal-catalysts.9-11 The C-H
amidation for ketone and aldehyde groups is challenging due
to their weak coordinating ability.12d
Although there are a few reports on the C-H amidation of
aldehydes using transient imine group, there are no reports on
the same reaction with ketones. The difficulty in using ketone
as a transient directing group is enolizabilty of ketones.
Changʼs group pioneered the transiꢀon metal-catalyzed C-H
amination reactions.8 The ortho-C-(sp2)-H amidation of
aldehyde with the different transition metals has been
reported under transient directing group strategy using aryl
sulphonyl azides and dioxazolone as an amidating reagent
under a harsh reaction conditions.12 Herein, we report the
ortho-C-(sp2)-H amidation of ketones and aldehydes using
Rh(III)-catalyst and dioxazolone as an amidating reagent. To
the best of our knowledge, this is the first report on the ortho-
C-(sp2)-H amidation of ketones using a transient directing
group. The ortho-C-(sp2)-H amidation of aldehyde under
ambient conditions using a transient directing group strategy is
also unprecedented.
The C-H bond activation for the formation of C-N bonds is of
great importance as they are atom-economical methods for
synthesizing heterocyclic compounds.1,2 Amongst the directing
groups, the transient directing groups offers an advantage of
avoiding the installation and removal of directing groups.3
Jun’s work4i on Rh-catalyzed transient imine as a directing
group for the hydroarylation of acetophenones has triggered
the work in this direction. Following Jun’s work, Kuninobu and
Takai have demonstrated Re-catalyzed annulations of aromatic
ketones.4h which was followed by others using Pd-catalysts.4
Quinoline scaffold occurs in a number of natural products,
and biologically active molecules.5 2-Amino carbonyl aromatic
compounds are the extortionate synthetic feedstocks known
for quinoline synthesis (Figure 1).6 Quinoline is synthesised
using Friedländer quinoline synthesis,7 skraup synthesis,
Niementowski quinoline synthesis, etc.7 Buchwald-Hartwig
cross-coupling reaction does not need pre-functionalized
arenes for the C-H amination reaction.8 The ortho-C-(sp2)-H
amination reaction using directing group strategy with various
transition metals is highly efficient and selective. An array of
The optimization studies began by reacting 1-(p-
tolyl)ethanone (2a), 3-phenyl-1,4,2-dioxazol-5-one (1a) and
3,5-bis(trifluoromethyl) aniline (L11, 20 mol%) in the presence
of [RhCp*Cl2]2 (5 mol%) and AgSbF6 as a chloride scavenger (20
mol%) in TFE as solvent at 100 °C, which furnished the
amidated product 3aa in 17% NMR yield (entry 1, Table 1).
Other catalysts such as [Ru(p-cymene)Cl2]2 and [Cp*Co(CO)I2]
did not afford the amidated product (entries 2 and 3).
[RhCp*(OAc)2] Catalyst, which afforded the amidated product
3aa in 32% was found to be the better catalyst over
[RhCp*(CH3CN)3](SbF6)2 and [RhCp*Cl2]2 (entries 4, 5, and 1).
Solvent screening studies revealed (entries 6-7), TFE to be a
suitable solvent as it furnished the amidated product in 32%
yield (entry 4). A brief ligand screening revealed that 3,5-
Figure 1. ortho-Aminocarbonyl Moiety as Synthetic Feedstock
bis(trifluoromethyl) aniline is
a suitable aniline for this
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012,
Karnataka, India. E-mail: prabhu@iisc.ac.in; Tel: +91 80 22932887
† Electronic Supplementary Informaꢀon (ESI) available: Experimental details,
compound characterization, NMR spectra. See DOI: 10.1039/x0xx00000x
transformation (see the SI, Table 2 for the screening of
anilines). Among the halide scavengers, AgPF6 was found to be
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Table 1 Reaction optimizationa
respectively. 4-Methoxy substituted acetophenone, having an
electron-donating substituent on the phenyl ring, afforded the
amidated product 3ae in 58% yield. The 3-
methylacetophenone furnished the amidated product 3af in
44% yield, whereas 4-bromoacetophenone afforded the
amidated product 3ag in 38% yield. The propiophenone
furnished 3ah in 46% yield.
entry catalyst (mol %)
Ag-salt
(equiv)
AgSbF6
AgSbF6
AgSbF6
AgSbF6
Additives
(mol %)
none
none
none
none
none
none
none
none
none
none
AcOH
NaOAc
none
none
none
none
none
none
Yieldb
(%)
17
nd
nd
32
5
1
[RhCp*Cl2]2
After optimizing the reaction conditions for ketones, we
explored the scope of the reaction for aldehyde derivatives
(Scheme 2). The optimal conditions for the amidation of
aldehydes was reached using 2-methylbenzaldehyde (4a, 1.0
equiv), dioxazolone 1a (1.2 equiv), 3,5-bis(trifluoromethyl)
aniline (L11, 20 mol %), Rh-catalyst (7.5 mol %), Ag salt (30 mol
%, TFE (2 mL) at rt, ( 48 h) (see ESI Tables 3 and 4 for screening
studies). It is noteworthy to mention that this is one of the rare
unprecedented C-H activation reaction at the ambient
conditions (see ESI Tables 3 and 4 for more details). The
reaction of 2-methylbenzaldehyde, benzaldehyde, 4-
2
3
4
[Ru(p-cymene)Cl2]2
[Cp*Co(CO)I2]
[RhCp*(OAc)2]
5
[RhCp*(CH3CN)3](SbF6) AgSbF6
[RhCp*Cl2]2
[RhCp*Cl2]2
6c
AgSbF6
AgSbF6
AgBF4
AgNTf2
AgPF6
AgPF6
AgPF6
AgPF6
AgPF6
AgPF6
AgPF6
AgPF6
AgPF6
7
5
7d
8
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
[RhCp*(OAc)2]
45
44
43
43
18
45
51
63
13
66
18
9
10
11
12
13e
14f
15g
16h
17i
18j
methylbenzaldehyde,
4-ethylbenzaldehyde,
4-
isopropylbenzaldehyde, and 4-tert-butylbenzaldehyde and 3-
methylbenzaldehyde with dioxazolone 1a furnished the
a
Reaction conditions: Unless otherwise noted, all reactions were carried out
corresponding amidated products 5aa, 5ab, 5ac, 5ad, 5ae, 5af,
using 1a (0. 24 mmol), 2a (0.2 mmol), ligand
Ag salt (0.04 mmol), additive (0.02 mmol), TFE (2 mL) as solvent. NMR yield.
L
(0.04 mmol), catalyst (0.01 mmol),
b
c
and 5ag in 77, 75, 71, 72, 71, 64, and 57% yields, respectively.
4-Methoxybenzaldehyde having an electron donating
substituent afforded the amidated product 5ah in 57% yield.
Benzaldehydes having electron-withdrawing ethyl ester
substituent at the para-position furnished the amidated
product 5ai in 59% yield. However, 4–nitrobenzaldehyde failed
to furnish the amidated product. The halogen-substituted
benzaldehydes such as 4-chlorobenzaldehyde and 4-
(trifluoromethyl)benzaldehyde furnished the corresponding
amidated products 5aj and 5ak in 48 and 57% yields,
respectively. Whereas the reaction of diaxazolone 1a with 4-
cyanobenzaldehyde did not afford the desired product. The
reaction of 1a with 3-phenoxybenzaldehyde and 3-
methoxybenzaldehyde afforded the corresponding amidated
products 5al and 5am in 60 and 69% yields, respectively. 2,4-
dimethoxybenzaldehyde, heliotropin, 2-acetoxybenzaldehyde,
DCE as solvent. d chlorobenzene as solvent, e 10 mol% of L11 f 50 mol% of L11
. .
g
50 mol% of L11 and 1 mL TFE was used. h 3 mL TFE was used. i 50 mol% of L11, 1
mL TFE, and AgPF6 10 mol%. j In the absence of aniline.
better halide scavenger (entries 4, 8-10) as the unreacted
starting material was more while using AgPF6. Acid additive,
AcOH, has no influence on the reaction, whereas NaOAc was
detrimental for the reaction (entries 11 and 12). Decreasing
the amount of aniline L11 to 10 mol% had no influence on the
reaction (45%, entry 13) while increasing the amount of L11 to
50 mol% enhanced the yield of 3aa to 51% (entry 14).
Increasing the concentration of the reaction mixture enhanced
the yield of 3aa to 63% (entry 15), whereas increasing the
dilution of the reaction decreased the yield of 3aa (13%, entry
16). The optimal conditions was reached using 10 mol% of
AgPF6 to obtain the product 3aa in 66% yield (entry 17).
However, in the absence of L11, the amidated product 3aa was
obtained in 18% yield (entry 18, see the ESI, Tables 1 and 2).
After optimizing the reaction conditions, the scope of the
reaction was explored for ketone derivatives (Scheme 2). 4-
Methylacetophenone, acetophenone, 4-ethylacetophenone,
and 4-tert-butylacetophenone afforded the amidated products
and 1-naphthaldehyde afforded the amidated products 5an
,
5ao
,
5ap, and 5aq in 58, 43, 50 and 78% yields, respectively.
O
O
O
H
O
L11 (20 mol %)
[RhCp*Cl2]2 (7.5 mol %)
N
R
H
R
O
+
NH
AgSbF6 (30 mol %)
TFE (2 mL), rt, 48 h
Ph
H
4
1a
5
O
Ph
3aa, 3ab, 3ac, and 3ad in 64, 62, 61, and 62% yields,
O
O
5ag, R = 4-Me, 57%
5ah, R = 5-OMe, 57%
5aa, R = 3-Me, 77%
5ab, R = H, 75%
H
H
R = 5-CO Et, 59%
2
5ai,
R
R
5aj, R = 5-Cl, 48%
5ac, R = 5-Me, 71%
5ad, R = 5-Et, 72%
5ae, R = 5-iPr, 71%
5af, R = 5-tBu, 64%
NH
NH
O
5ak, R = 5-CF3, 57%
5al, R = 6-OPh, 60%
5am, R = 6-OMe, 69%
R = 5-NO2 and 5-CN, nd
O
Ph
O
Ph
O
OAc
O
O
O
Ph
O
NH
O
H
H
H
H
NH
O
NH
NH
5an, 58%
5ap, 50%
3aq, 78%
5ao, 43%
O
O
Ph
O
Ph
O
Ph
Scheme 3. Scope of the Amidation Reaction with Aldehydesa. Reaction conditions: 1a
Scheme 2. Scope of the amidation reaction with ketone. Reaction conditions: 1a (0.24
mmol), 2 (0.2 mmol). nd = not detected.
(0.24 mmol), 4 (0.2 mmol). nd = not detected.
2 | J. Name., 2012, 00, 1-3
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The scope of the reaction was also explored using 2-
methylbenzaldehyde 4a with variety of dioxazolone
a
derivatives (Scheme 4). The reaction of 4a with 3-(p-Tolyl)-
1,4,2-dioxazol-5-one, 3-(4-fluorophenyl)-1,4,2-dioxazol-5-one,
3-(4-chlorophenyl)-1,4,2-dioxazol-5-one
(trifluoromethyl)phenyl)-1,4,2-dioxazol-5-one afforded the
corresponding amidated products 5ba 5ca 5da, and 5ea in 57,
and
3-(4-
,
,
62, 61, and 73% yields, respectively. Dioxazolones having
electron-withdrawing substituents at the para-position of the
phenyl
ring
of
dioxazolone
such
as
3-(4-
3-(4-
(trifluoromethyl)phenyl)-1,4,2-dioxazol-5-one
and
nitrophenyl)-1,4,2-dioxazol-5-one afforded the amidated
products 5ea and 5fa in 73 and 77% yields, respectively. 3-(4-
Methoxyphenyl)-1,4,2-dioxazol-5-one, which has an electron-
donating substituent at the para-position of the phenyl ring of
dioxazolone, furnished the amidated product 5ga in low yield
(9%). 3-(m-Tolyl)-1,4,2-dioxazol-5-one and 3-(3-chlorophenyl)-
1,4,2-dioxazol-5-one dioxazolone afforded the corresponding
amidated products 5ha and 5ia in 59 and 65% yields,
respectively. The β-naphthyl substituted dioxazolone, 3-
(naphthalen-2-yl)-1,4,2-dioxazol-5-one furnished the amidated
product 5ja in 36% yield. The reaction of 4a with 3-(2-
Scheme 5. Synthetic Utility: Synthesis of Indoloquinoline Alkaloids Quindolinone
and Cryptolepine Analog
To get an insight of the reaction, we performed a few
control experiments (Scheme 6). A competitive reaction of
electron-donating 4-methoxyaniline
(
L3
)
and electron-
L11 with 2-
and 10 in a
withdrawing 3,5-bis(trifluoromethyl)aniline
(
)
methylbenzaldehyde 4a furnished the imines
ratio of 1.0:0.09 (see 1H NMR spectrum ESI-111). This reaction
9
suggests that the formation of imine 10 is slower than the
imine
9
, and the imine 10 forms the rhodacylce effectively
. The deuterium incorporation experiment of 2b
fluorophenyl)-1,4,2-dioxazol-5-one
and
3-(3-Methyl-4-
than imine
9
nitrophenyl)-1,4,2-dioxazol-5-one yielded the aminated
products 5ka and 5la in 62 and 77% yields, respectively.
Heterocyclic dioxazolone, 3-(thiophen-3-yl)-1,4,2-dioxazol-5-
one, afforded the amidated product 5ma in 39% yield. The
reaction of 4a with aliphatic dioxazolone, 3-nonyl-1,4,2-
dioxazol-5-one, furnished the product 5na in 75% yield.
furnished deuterium incorporation at the ortho-position of the
acetophenone 2b in 11%, indicating C-H activation occurs at
the ortho-position via a five-membered metallacycle (see ESI
for 1H NMR spectra SI-112). Further, the intermolecular
competitive experiment with acetophenone 2b and deutrio 2b
with diaxazolone 1a suggests the kinetic isotopic effect value
1
of 2.2 (Scheme 5 and see the ESI for H NMR spectra SI-113-
114). This reaction suggests that the C-H activation is the
turnover-limiting step for the amidation, and the C-H
activation by Rh(III)-catalyst could be a reversible process.
Scheme 4. Scope of Dioxazolone Derivatives for the Amidation
Scheme 6. Preliminary Mechanistic Studies
To demonstrate the synthetic utility of this protocol, N-(2-
Based on the literature precedences14 and control
experiments, a tentative mechanism has been proposed
(Scheme 7). Rh(III)-catalyst in the presence of Ag-salt forms an
formyl-3-methylphenyl)benzamide
(
5aa
)
was transformed
into olefinated products 6a and 6b in 84 and 83% yields,
respectively (Scheme 5). The reaction of amidated product 5ab
with
tetrahydroquinolinone derivative
enamine catalysis conditions. The α-iodo-aminocyclization of
followed by the hydrolysis furnished the alkaloid Quindolinone
in 66% yield (Scheme 4). This alkaloid can be converted
into Cryptolepine alkaloid analog over three consecutive
2-amino
acetophenone
furnished
4-
active Rh(III)-catalyst
I, which undergoes reversible C-H
7
in 37% yield under
activation to form a five-membered rhodacycle II through a
concerted metallation-demetallation just after the imine
formation. The coordination of the dioxazolone with II forms a
metal complex III, through ligand exchange. Extrusion of CO2
and subsequent intermolecular migratory insertion through a
7
8
8
9
steps.13 These indoloquinoline alkaloids show antimalarial
activity and have potent antiplasmodial activity.13
seven-membered rhodacycle forms IV
protodemetallation of IV in the presence of imine of
the amidated product (Scheme 6).
.
Finally, the
2
leads to
3
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6
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Scheme 7. Proposed mechanism
In summary, a Rh(III)-catalyzed ortho-C-(sp2)-H amidation
of ketones and aldehydes has been achieved using dioxazolone
as an amidating reagent. To the best of our knowledge, this is
the first report for amidation of ketones under transition
metalcatalysis. This transient directing group strategy for
aldehydes works at ambient conditions. Synthesis of
indoloquinoline alkaloids demonstrated the application of this
amidation method.
9
(a) A. E. Hande and K. R. Prabhu, J. Org. Chem., 2017, 82
13405-13413. (b) A. E. Hande, N. Muniraj and K. R. Prabhu,
ChemistrySelect 2017, 5965-5969. (c) P. Becker, R.
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2
,
This work was supported by SERB (EMR/2016/006358),
New-Delhi, CSIR (No. 02(0226)15/EMR-II), New-Delhi, Indian
Institute of Science, RL Fine Chem, Bangalore and Synovation
Chemicals and Sourcing Pvt Limited, Bangalore. We thank Dr.
A. R. Ramesha (RL Fine Chem) for useful discussions. A. H.
thanks CSIR, New Delhi, for a senior research fellowship.
,
15493-15496. (d) C. Pi, X. Cui and Y. Wu, J. Org. Chem. 2015,
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Conflicts of interest
There are no conflicts to declare.
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