RhIII-Catalyzed Decarboxylative o-Acylation of Arenes Bearing an Oxidizing Directing Group

Article abstract of DOI:10.1002/ejoc.201900242

Here in we report, rhodium(III)-catalyzed decarboxylative acylation of arenes using α-oxocarboxylic acids as acyl surrogate. In this strategy, O–NHAc group act as an autocleavable oxidizing directing group (ODG^auto), thus giving rise to ortho-acylated phenols in moderate to good yields. Mechanistic studies provided strong support for a kinetically relevant C–H bond activation. According to the best of our knowledge, this is the first report of Rhodium catalyzed decarboxylative acylation.

Full text of DOI:10.1002/ejoc.201900242

A Journal of
Accepted Article
Title: Rh(III)-Catalyzed Decarboxylative o-Acylation of Arenes Bearing
an Oxidizing Directing Group
Authors: Suvankar Bera, K. Chandrasekhar, Satadru Chatterjee, Sunil
Kumar Killi, Debabrata Sarkar, and Biswadip Banerji
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201900242
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10.1002/ejoc.201900242
European Journal of Organic Chemistry
COMMUNICATION
Rh(III)-Catalyzed Decarboxylative o-Acylation of Arenes Bearing
an Oxidizing Directing Group
Suvankar Bera,a K. Chandrasekhar,a,b Satadru Chatterjee,a Sunil Kumar Killi,a Debabrata Sarkar, a
Biswadip Banerji,*a,b
Abstract : Here in we report, Rhodium(III)-catalyzed decarboxylative
acylation of arenes using α-oxocarboxylic acids as acyl surrogate. In
this strategy, ONHAc group act as an autocleavable oxidizing
directing group (ODGauto), thus giving rise to ortho-acylated phenols
in moderate to good yields. Mechanistic studies provided strong
support for a kinetically relevant CH bond activation. According to
our knowledge, this is the first report of Rhodium catalyzed
decarboxylative acylation.
functionalization to access phenol,11 we aimed to synthesize
ortho-acylated phenols via Rh(III)-catalyzed direct CH acylation
of arenes bearing O−NHAc group as ODGauto
. Phenols
containing acyl group are considered as significant structural
motifs for their great abundance in diverse type of bio-active
molecules including natural products12 (Figure 1). Among the
family of acyl group assisted phenols, o-acyl phenols are most
important for their wide range of application. They serve as the
prime building blocks for the synthesis of various drugs such as
celiprolol, acebutolol, warfarin, propafenone etc.13 In addition to
this, o-acylated phenols are effecttive synthetic intermediates to
access various types of oxygen-containing heterocyclic scaffolds
such as benzoxazole, benzofuranone, dibenzoxazepine and
chromanone etc. Therefore, development of a method for the
preparation of ortho-acyl phenols is always appreciated.
Introduction
Transition-metal-catalyzed chemical transformation of CH bond
has emerged as a highly focused area of research to the
synthetic community since last few decades. Diverse types of
CH bond functionalization have been explored intensely. Acyl
functionalization to CH bond always draw considerable
attention due to the large abundance of acyl group in the family
of organic molecular systems. In the recent years, α-
oxocarboxylic acids have been explored as efficient acyl
surrogates for acylation to CH bond of aryl systems containing
diverse types of directing groups such as pyridines,1
acetanilides,2 azoarene,3 O-methyl ketoximes,4 amides,5 N-
nitrosoanilines6 etc. These methods produce CO2 as the waste
instead of often toxic species. Goossen was the pioneer person
to develop a synthetic route to achieve aryl ketones via Pd-
catalyzed decarboxylative cross coupling using aryl halides with
potassium α-oxocarboxylates in the presence of a Cu(I) source.7
After this pioneering work, several groups have reported CH
acylation through Pd-catalyzed decarboxylation of α-
oxocarboxylic acids. But there is no report of Rhodium catalyzed
decarboxylative acylation. Now, the catalytic activity changes
altering the transition metal. Specific transition metal is required
for a particular type of CH bond transformation. Thus any kind
of new catalytic activity of any transition metal always draw
considerable attention. In past few years, Rhodium or Iridium-
catalyzed various kinds of aryl CH functionalization have been
Figure 1. Some Bio-active Molecules Containing o-Acyl phenol
The traditional methods involved in synthesis of o-acylated
phenols (like Friedel- Craft acylation, Fries Rearrangement)14,15
suffer from various kinds of drawbacks such as lack of
regioselectivity or harsh reaction condition etc. Since, last few
decades direct CH functionalization technique has become
complementary to the classical protocols. So, accessing o-acyl
phenol through CH functionalization is in focus now a days to
overcome the problems of classical methods. Recently transition
metal catalyzed direct ortho-hydroxylation of aromatic ketone
has been explored for the preparation of o-acyl phenols but this
approach also suffers from site selectivity in few cases of bi-aryl
ketones.16 Therefore synthesis of o-acyl phenols via direct CH
transformation is expected to have the potential to draw
considerable attention.
reported using auto cleavable oxidizing directing group (ODGauto
)
such as CONHOMe,8 NNHR,9 ONHAc.10 These types of
directing groups, become traceless in the products to generate
valuable functional groups. In case of traditional directing
groups(DG) mediated CH functionalization, generally very
harsh conditions are required for removal of the DG after CH
functionalization to achieve the target molecule, whereas use of
auto cleavable DG’s circumvent the harsh conditions.
Results and Discussion
However, our investigation started with exploring the coupling of
N-phenoxyacetamide, 1a (1 equivalent) with phenylglyoxylic acid,
2a (1.2 equivalent) in the presence of 4 mol % [Rh(Cp*Cl2)]2
and 2 equivalent Cu(OAc)2 as an oxidant along with 1 equivalent
of CsOAc as an additive in acetonitrile solvent with constant
heating at 120 oC for 24 hours. This condition provided 7%
combined yield of mono (3a) and bis-ortho-acylated phenol (4a)
in 5:1 ratio (Table 1, entry 1). Next, we screened the solvent
system where only in DMF, the combined yield increased to a
very little extent (12%) with 4:1 ratio of mono & bis-ortho-
acylated product. Then we optimized the reaction condition with
different oxidizing agents. Oxidants like TBHP, CAN, K2S2O8 did
not give the desired product. Gratifyingly, we found Ag2CO3 (20
In accordance with the above information and inspired by the
recent advances in transition-metal-catalyzed C−H
[a] Organic & Medicinal Chemistry Division, Indian Institute of ChemicalBiology
(CSIR-IICB), 4 Raja S. C. Mullick Road, Kolkata 700032, India
[b] Academy of Scientific and Innovative Research (AcSIR),4 Raja S. C.
Mullick Road, Kolkata 700032, India
E-mail: biswadip.banerji@gmail.com
http://iicb.res.in/divisionwiselistofscientists/chemistry/biswadipb.html
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10.1002/ejoc.201900242
European Journal of Organic Chemistry
COMMUNICATION
mol%) with stoichiometric amount of K2S2O8 (1.5 - 2 equivalent)
to be the superior oxidizing system over other oxidants
producing the highest yield (Table 1, entry 10 - 11). The
combination of Ag2CO3 with other oxidants like TBHP, CAN,
Oxone did not satisfied the reaction condition. However, 20
mol% Ag2CO3 with 2 eq. K2S2O8 produced 84% combined yield
of mono- and bis-ortho-acylated phenol in 2.8 : 1 ratio.
To improve the selectivity towards mono-acylation the
amount of K2S2O8 was reduced to 1.5 equivalent from 2
equivalent and as a result the ratio of mono-and-bis product
was turned to almost 3.2 : 1 with 78% combined yield.
Using DMSO as sovent, the yield was not improved and
Both of [IrCp*Cl2]2 and [Rh(COD)Cl]2 as the catalyst instead
of [RhCp*Cl2]2 were unable to promote the reaction. We
also made an attempt to achieve the bis-ortho-acylated
product in major. To serve this issue, a reaction was carried
out using N-phenoxyacetamide, 1a (1 equivalent) with
phenylglyoxylic acid, 2a (3 equivalent) in the presence of 5
mol % [Rh(Cp*Cl2)]2 and 100 mol % Ag2CO3 with 2 eq.
K2S2O8 as the combined oxidant along with 1 equivalent of
CsOAc as additive in DMF solvent at 120 oC for 24 hours.
Table 1: Optimization of Reaction Conditionsa
En
try
Catalyst
Oxidant
Solvent
Yield
(%)c
Ratio
(3a : 4a)d
Table 2 : Substrate Scope for o-acyl phenol preparation
1. [RhCp*Cl2]2
2. [RhCp*Cl2]2
3. [RhCp*Cl2]2
4. [RhCp*Cl2]2
5. [RhCp*Cl2]2
6. [RhCp*Cl2]2
7. [RhCp*Cl2]2
Cu(OAc)2 (2 eq)
Cu(OAc)2 (2 eq)
Cu(OAc)2 (2 eq)
TBHP (2 eq)
MeCN
MeOH
DMF
DMF
DMF
DMF
DMF
7 %
0
5 : 1
---
12%
0
4 : 1
---
CAN (2 eq)
0
---
En-
try
N-Aryloxy
acetamide
-Oxocarboxylic
acid
Products
Yield%
(3:4)
K2S2O8 (2 eq)
0
---
AgOAc (20 mol%)
K2S2O8 (2 eq)
27 %
3 : 1
8. [RhCp*Cl2]2
9. [RhCp*Cl2]2
10. [RhCp*Cl2]2
11. [RhCp*Cl2]2
AgNO3 (20 mol%)
K2S2O8(2 eq)
DMF
DMF
DMF
DMF
DMF
DMSO
DMF
DMF
DMF
DMF
DMF
DMF
55 %
75 %
84 %
78 %
72 %
43 %
0
2.7 : 1
1a R = H
2a R1 = Ph
3a + 4a
3b
78 % (3.2 : 1)
73 %
1b R = o-Me
1c R = m-Me
2a
2a
2a
2a
2a
2a
2a
Ag2O (20 mol%)
K2S2O8(2 eq)
2.8 : 1
2.8 : 1
3.2 : 1
3 : 1
2.8 : 1
---
3c
79 %
1. 1d R = m-OMe
1e R = m-Ph
3d
82 %
Ag2CO3 (20 mol%)
K2S2O8 (2 eq)
3e
75 %
1f R = m-CF3
3f
78%
Ag2CO3 (20 mol%)
K2S2O8 (1.5 eq)
1g R = p-CF3
3g
76 %
1h R = p-CO2Me
3h
62 %
12. [RhCp*Cl2]2 Ag2CO3(20 mol%)
(NH4)2S2O8 (1.5eq)
1f
1f
2b R1 = p-Tolyl
3i
3j
83%
61 %
65%
13. [RhCp*Cl2]2 Ag2CO3 (20 mol%)
K2S2O8 (1.5 eq)
2c R1 = p-Fluorophenyl
2d R1 = p- Chlorophenyl
2e R1 = p- Bromophenyl
2f R1 = 2-Furyl
2. 1f
1f
3k
3l
14. [RhCp*Cl2]2 Ag2CO3 (20 mol%)
TBHP (1.5 eq)
78 %
67 %
1f
3m
15. [RhCp*Cl2]2 Ag2CO3 (20 mol%)
CAN (1.5 eq)
0
---
3. 1d
2g R1 = Isobutyl
3n
51 %
16. [RhCp*Cl2]2 Ag2CO3 (20 mol%)
Oxone (1.5 eq)
0
---
1a R = H
2a R1 = Ph
2a R1 = Ph
2a R1 = Ph
2a R1 = Ph
4a
4b
4c
4d
83 %
88 %
85 %
79 %
17. [IrCp*Cl2]2
Ag2CO3 (20 mol%)
K2S2O8 (1.5 eq)
0
---
4. 1i R = p-Me
1j R = p-tBu
18. [Rh(COD)Cl]2 Ag2CO3 (20 mol%)
K2S2O8 (1.5 eq)
0
---
1k R = p-Ph
19. [RhCp*Cl2]2
Ag2CO3 (1 eq)
K2S2O8 (2 eq)
83 % 1 : 20
aReaction Conditions for mono-Acylation (from 3a to 3n): N-
phenoxyacetamide (0.2 mmol), α-oxocarboxylic acid (0.24 mmol),
[RhCp*Cl2]2 (4 mol %), Ag2CO3 (20 mol%) + K2S2O8(1.5 eq), CsOAc (1
eq.), DMF (2mL), 120oC, 24 h in sealed tubes. bReaction Conditions for
bis-Acylation (from 4a to 4d): N-phenoxyacetamide (0.2 mmol), α-
oxocarboxylic acid (0.6 mmol), [RhCp*Cl2]2 (5 mol %), Ag2CO3 (1 eq.) +
aReaction Conditions: 1a (0.2 mmol), 2a (0.24 mmol), [RhCp*Cl2]2 (4 mol %),
oxidant (quantity noted), CsOAc (1 eq.), solvent (2 mL), 120 oC, 24 h in sealed
tubes. bCondition: 1a (0.2 mmol), 2a (0.6 mmol), [RhCp*Cl2]2 (5 mol %),
oxidant (quantity noted), CsOAc (1 eq.), solvent (2 mL), 120 oC, 24 h in sealed
c
K2S2O8 (2 eq), CsOAc (1 eq.), DMF (2mL), 120oC, 24 hr. Yield isolated
c
tube. Combined Yields of 3a and 4a. dRatio of 3a and 4a was determined by
1HNMR analysis of crude reaction mixture.
by column chromatography.
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10.1002/ejoc.201900242
European Journal of Organic Chemistry
COMMUNICATION
transformed (3c / 3f = 1:9), suggesting that the C−H activation
process might follow a concerted metalation−deprotonation
(CMD) mechanism.17
Remarkably, this reaction condition provided the ratio of
mono- and bis-ortho-acylated phenol nearly to 1 : 20 with
83 % combined yield.
Subsequently, the coupling reaction between N-methyl-
substituted phenoxyacetamide 1l and phenylglyoxylic acid 2a
was carried out under standard mono-acylating condition
(Scheme 1d) but this reaction did not produce the desired
product. This fact indicates that the N–H bond of O–NHAc is
indispensable for this transformation which is consistent with the
previous reports of Lu18 and Yi.11e
Thereafter, the substrate scope was explored using the
optimized reaction condition. It is interesting to note that the
N-phenoxyacetamides bearing strong electron withdrawing
groups (1g, 1h : CF3, CO2Me) at the para-position afforded
exclusively mono-acylated compounds 3g, 3h in
satisfactory yield (Table 2). In addition, the reaction of
meta-substituted
N-
aryloxyacetamides
exclusively
occurred at the more sterically accessible position to afford
the corresponding mono-acylated phenol as a single
product. These data suggest that steric effects of the
substrate strongly interfere with either the formation of the
cyclometalated intermediate or the proximity of α-
oxocarboxylic acid to the cyclometalated intermediate. The
ortho-substituted N-aryloxyacetamides are also compatible
to the reaction condition.
Scheme 1 : Mechanistic Studies
Next, we aimed to achieve bis-ortho-acylated phenols for
the N-aryloxyacetamides bearing electron donating groups
at para-position using the reaction condition for bis-
acylation(Table
1,
entry
19).
Symmetrical
N-
phenoxyacetamides (1 equivalent) with methyl, tert-butyl
and phenyl group at the para-position (1i, 1j, 1k) underwent
smooth bis-acylation reaction producing the corresponding
bis-acylated products 4b, 4c, 4d with high yield (Table 2).
But surprisingly, this bis-acylating condition was unable to
generate bis-acylated product for the N-phenoxyacetamides
bearing strong electron withdrawing groups like CF3,
CO2Me (1g, 1h) at the para-position. The scope of α-
oxocarboxylic acids was also explored. Arylglyoxylic acid
with electron donating group was favourable in comparison
to arylglyoxylic acid substituted with electron withdrawing
group. Hetero-arylglyoxylic acids and aliphatic-glyoxylic
acids are also suitable for this methodology. Different types
of arylglyoxylic acids were prepared by well known Riley
oxidation method: oxidation of corresponding acetophenone
(a) kinetic isotope study for mono-acylation. (b) kinetic isotope study for
bis-acylation. (c) Competitive experiment. (d) Replacing ONHAc group
by ONMeAc. (e) Necessity of ONHAc group for bis-acylation
Then, 3a was subjected to couple with phenylglyoxylic acid 2a
to evaluate the necessity of O–NHAc group for the second o-
acylation during bis-acylation and this time also no
transformation of 3a happened (Scheme 1e). This indicates that
the ON bond of the oxidizing directing group is cleaved after
acyl functionalization i.e. these two processes are not concerted.
It is believed that this transformation begins with the ortho-
metallation of N-aryloxyacetamide with Rh(III) to provide the five
membered Rhodacycle B which undergoes a transmetalation
step with acyl-silver species formed by the silver mediated
decarboxylation of α-oxocarboxylic acids to afford complex C.
Thereafter, reductive elimination of C provides the aryl-acylated
intermediate D and Rh(I). Finally, Rh(I) get reoxidized to Rh(III)
by the oxidizing directing group itself and consequently the
directing group is being cleaved to generate the hydroxyl
functional group (Scheme 2).
derivatives using selenium dioxide as oxidant.
Next, a set of experimental investigations were conducted to
explore the deep insight of the reaction mechanism. First, the
isotope-labeling experiment was carried out with deuterium-
labeled N-phenoxyacetamide [D5]-1a.
Treatment of 2a with the equimolar amount of both 1a and [D5]-
1a for 2 hours under standard mono-acylating condition gave a
relatively large KIE value (kH/kD = 3.3). The result indicated that
the cleavage of C–H bond might be involved in the rate-
determining step (Scheme 1a). Thereafter, same amount of both
1a and [D5]-1a were treated with 2a for 2 hours under bis-
acylating condition and this experiment resulted greater KIE
value (kH/kD = 4.8) than earlier experiment which supports the
fact considering the C–H bond cleavage to be involved in the
rate-limiting step.11e
Next, to delineate the electronic preference of the reaction a
competitive coupling between an equimolar amount of 1c and 1f
with 2a was conducted (Scheme 1c). The ratio of products
showed that the electron-deficient 1f was preferentially
It may be considered that bis-acylated phenols are formed
when the mono acylated N-aryloxyacetamides become involved
again in carbometalation process with remaining Rhodium-(III) at
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Conclusions
In summary, we have developed a new Rhodium(III)-catalyzed
decarboxylative strategy for ortho-CH acylation of arenes,
associated with autocleavable oxidizing directing group
(ODGauto) to achieve o-acylated phenols. As per our knowledge,
this is the first report for Rh(III)-catalyzed decarboxylative
acylation. Our ongoing studies need to focus over the
unexplored area based on redox neutral CH acylation.
Acknowledgments
S.B, K.C, S.K.K thank CSIR, India for a senior research
fellowship and S.C thanks UGC for a senior research fellowship
and D.S thanks DST for a junior research fellowship . We thank
Mr. E. Padmanaban, CSIR-IICB, for NMR and Mr. Sandip
Chakraborty, CSIR-IICB, for recording the HRMS.
The authors declare no competing financial interest .
Keywords: CH Activation • CC Coupling • Acylation •
Homogeneous Catalysis
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10.1002/ejoc.201900242
European Journal of Organic Chemistry
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Rh(III)-Catalyzed Decarboxylative Acylation
TOC Text : It is the first report for Rh(III)-Catalyzed Decarboxylative Acylation of arenes. This
method provides an efficient access to both of mono/bis-ortho acylated phenols selectively. In general,
for para-substituted N- aryloxyacetamides, the product selectivity towards mono and bis-acylated
phenols can be controlled by varying the amount of oxidant. But ortho- and meta- substituted N-
aryloxyacetamides give exclusive mono-acylated product at any condition.
.
This article is protected by copyright. All rights reserved.