Copper porphyrin as efficient catalysts for esterification of allyl sp3 C–H bond with carboxylic acid

Article abstract of DOI:10.1016/j.catcom.2019.04.001

We described that copper 5,10,15,20-tetrakis (ethoxycarbonyl)porphyrin (TECP) catalyzed oxidative cross dehydrogenative coupling of allyl sp³ C–H bond with acid for the synthesis of allyl esters in a homogeneous system. This reaction proceeded

Full text of DOI:10.1016/j.catcom.2019.04.001

Accepted Manuscript
Copper porphyrin as efficient catalysts for esterification of allyl
sp3 C-H bond with carboxylic acid
Ming-Feng Xiong, Atif Ali, Waseem Akram, Hao Zhang, Li-Ping
Si, Hai-Yang Liu
PII:
S1566-7367(19)30109-8
DOI:
Reference:
https://doi.org/10.1016/j.catcom.2019.04.001
CATCOM 5669
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
26 December 2018
29 March 2019
1 April 2019
Please cite this article as: M.-F. Xiong, A. Ali, W. Akram, et al., Copper porphyrin as
efficient catalysts for esterification of allyl sp3 C-H bond with carboxylic acid, Catalysis
Communications, https://doi.org/10.1016/j.catcom.2019.04.001
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ACCEPTED MANUSCRIPT
Copper Porphyrin as Efficient Catalysts for Esterification of
Allyl sp3 C–H Bond with Carboxylic Acid
Ming-Feng Xiong a, Atif Ali a, Waseem Akram a, Hao Zhanga, Li-Ping Si *b, Hai-Yang Liu*a
a Department of Chemistry, Key Laboratory of Functional Molecular Engineering of Guangdong
Province, South China University of Technology, Guangzhou 510641, China
b School of Materials Science and Energy Engineering, Foshan University, Foshan 528000, China
ABSTRACT
We described that copper 5,10,15,20-tetrakis (ethoxycarbonyl)porphyrin (TECP) catalyzed
oxidative cross dehydrogenative coupling of allyl sp3 C–H bond with acid for the synthesis of allyl
esters in a homogeneous system. This reaction proceeded with broad substrate scope and good
functional group tolerance. In the gram-level test, the turnover number (TON) reached to 8100 at
0.01 mol% catalyst loading, with 81% yield.
Keywords: Porphyrin, Copper, Cross dehydrogenative coupling, Allylic esterification
1. Introduction
Allylic esters are versatile key motifs with extensive applications in synthesis and importantly
as ubiquitous cores in many natural products [1], pharmaceutical molecules, and fine chemicals [2,
3]. Therefore, continuous interests have been shown in the access of efficient, convenient,
straightforward, and highly atom-economic methods for the synthesis of allylic esters through C-X
(C, O, N, etc.) bond construction in recent years [2, 4]. The synthesis of allylic esters by direct
oxidative cross dehydrogenative coupling (CDC) using allylic C–H substrates and acids as the
starting materials is more atom-economic than by tandem C–H oxidative esterification between
acid precursors (aldehydes, arylmethanes, alkenes, or alkynes) and alkenes [5-7]. Many transition
metal catalysts such as iron [8], cobalt [9], copper [10, 11], copper-aluminum [12], and
tetrabutylammonium iodide [13] have been developed for the esterification of allylic sp3 C–H
bond. However, the catalyst loadings are generally higher than 10 mol% in these systems and with
the drawback of poor regioselectivity, diastereoselectivity, and enantioselectivity.
Metal porphyrin complex, as a bioinspired catalyst [2, 14], exhibits remarkable catalytic
efficiency in many reactions such as oxidation [14, 15], radical hydrofunctionalization of olefins
[16], nitrene [17], alkylation [18], carbene C–H insertions, and asymmetric synthesis [19-21].
Much efforts have been made to enhance the catalytic efficiency [22], regioselectivity [23],
diastereoselectivity, and enantioselectivity [20] to achieve a significant breakthrough in these
reactions. Despite that metal porphyrin-catalyzed reactions are very well documented, the
utilization of metal porphyrin catalysts in CDC reactions is rarely explored. In 2013, Che and his
co-workers used Pd (II) porphyrin as a catalyst (0.05 mol%) in the photochemical CDC reaction of
tertiary amines and dimethyl malonate or diethyl phosphite [22]. Two years later, Guo had also
reported the application of copper porphyrin to achieve aerobic oxidative CDC of terminal alkynes

ACCEPTED MANUSCRIPT
[24]. Yuan reported cobalt corrolazine-catalyzed aerobic CDC of sp2 C-H and thiols for C-S bond
formation in water [25]. 5,10,15,20-Tetrakis (ethoxycarbonyl)porphyrin (TECP) is a kind of
electron-deficient flat macrocyclic ligand [26, 27]. Manganese TECP was found recyclable with a
high conversion efficiency in the oxidation of styrene using TBHP as oxidant [28]. Recently, we
had successfully used TECP copper [29] and iron [30] complex in (CDC) esterification reaction
between 1,4-dioxane C(sp3)–H and carboxylic acids. To further our study along this line, here we
report the CDC esterification reaction between allyl C(sp3)–H and benzoic acid derivatives.
Manganese, iron, cobalt, nickel, copper, palladium, and silver TECP complexes had been used in
the screening tests (Scheme 1), of which only iron and copper TECP exhibited catalytic activity.
Surprisingly, in the gram-level test, when CuTECP catalyst loading was 0.01 mol% using DTBP
as oxidant at 100 ℃ for 72 h, TON of oxidative coupling of benzoic acid and cyclohexene sp3
C–H bonds was up to 8100 with 81% yield, demonstrating the highest TON of this reaction
recorded thus far [8-10, 12, 13]. Furthermore, we had also checked the scope of benzoic acid
derivatives and regioselectivity of allylic esterification by using asymmetric olefins.
M=Mn, Fe, Co, Ni, Cu, Pd, Ag
Scheme 1. Molecular structure of metal TECP
2. Experimental Procedures
2.1 Materials and methods
All reagents were of commercial grade and purified according to the established procedures,
and solvents were of analytical purity. Extracts were dried over anhydrous sodium sulfate. All
solvents were concentrated in a rotary evaporator under vacuum, and the resulting residue was
purified using a silica gel column. UV–Visible absorption spectra were measured using a Hitachi
3900H spectrometer in a quartz cell of 1 cm optical path length at room temperature. NMR spectra
1
were recorded in CDCl3 with tetramethylsilane as the internal standard for H NMR (400 MHz)
and 13C NMR (100 and 150 MHz). HRMS spectra were recorded using a Bruker maXis impact
mass spectrometer with an ESI source.
2.2 Synthetic procedure
Benzoic acids 1 (0.5 mmol), alkene 2 (5 mmol), DTBP (1 mmol), CuTECP (0.1 mol%), and
benzene (1 mL) were added to a Schlenk tube and stirred at 100 ℃ for 24 h. The reaction mixture
was concentrated to remove solvent in a rotary evaporator after the Schlenk tube was cooled to
room temperature. The crude products were purified by silica gel (300-400 mesh size) column

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chromatography (hexane/ethyl acetate = 50:1).
3. Results and discussion
Table 1
Optimization of Reaction Condition. a
Entry
1
Cat. (mol%)
CuTECP (2.5)
CuTECP (0.5)
CuTECP (0.1)
CuTECP (0.01)
CuTECP (0.5)
CuTECP (0.5)
CuTECP (0.5)
CuTECP (0.5)
CuTECP (0.5)
FeTECPCl (0.5)
(FeTECP)2O (0.5)
AgTECP (0.5)
MnTECPCl (0.5)
CoTECP (0.5)
NiTECP (0.5)
PdTECP (0.5)
Oxidant (equiv.) time (h)
Yield b
99%
TON
39.6
190
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
TBHP (2.0)
m-CPBA (2.0)
Oxone (2.0)
PhIO (2.0)
4
2
12
24
72
12
12
12
12
12
12
12
12
12
12
12
12
12
95%
3
91%
910
4
80%
8000
100
5
50%
6
N.D. c
N.D.
N.D.
N.D.
80%
7
8
9
H2O2 (2.0)
10
11
12
13
14
15
16
17
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
DTBP (2.0)
160
150
75%
Trace
Trace
Trace
Trace
Trace
N.D.
a Reaction condition: benzoic acid (0.5 mmol), cyclohexene (5 mmol), catalyst CuTECP (0.1 mol%),
and benzene (1 mL) at 100 ℃ for 24 h. b isolated yield based on carboxylic acid. c not detected. DTBP
=
di-tert-butyl peroxide. TBHP = tert-butyl hydroperoxide (70% in H2O). m-CPBA =
3-chloroperbenzoic acid. H2O2 (30% in H2O). Oxone = potassium peroxymonosulfate.
As seen in Table 1, the oxidative dehydrogenation coupling of benzoic acid and cyclohexene
was selected as a model to investigate the catalytic activity of MTECPs (M = Mn, Fe, Co Ni, Cu,
Pd, and Ag). Cyclohex-2-en-1-yl benzoate was observed to be the main product when FeTECPCl
or CuTECP was used as the catalyst at 100 ℃ and DTBP as the oxidant. When the catalyst

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loading of CuTECP was 2.5 mol% (vs. benzoic acid), 1a was obtained with an isolated yield of 99%
in 4 h (Table 1, entry 1). When the concentration of catalyst loading was decreased to 0.5 mol%,
the isolated yield of 1a still reached to 95% after 12 h (Table 1, entry 2). To our surprise, the
reaction of acid and cyclohexene in the presence of a catalytic amount of CuTECP (0.1 mol%)
produced 2-cyclohexenyl benzoate 1a with a yield of 91% in 24 h (Table 1, entry 3). These
preliminary results motivated us to further decrease the catalyst loading to 0.01 mol%, and we
found that 1a was still obtained with an 80% yield with 8000 TON (Table 1, entry 4). Using TBHP
instead of DTBP, the yield sharply dropped to 50% (Table 1, entry 5). When TBHP was replaced
with some stronger oxidants such as m-CPBA, Oxone, PhIO, H2O2, and PhI(OAc)2, no products
were detected and the substrates were completely decomposed (Table 1, entries 6–9). When Mn,
Fe, Co, Ni, Pd, and Ag-TECP catalysts were employed to catalyze the reaction with 0.5 mol%
catalyst loading, only FeTECPCl and FeTECP-µ-oxo afforded 1a with 80% and 75% yield,
respectively. The other M-TECP complexes yielded trace product (Table 1, entries 10-16). As seen
in Table S1, when catalysts were copper chloride and copper acetate with the same catalyst
loading (0.1 mol%), the yield of 1a was 21% and 25%, respectively. When CuTPP was used as the
catalyst, 63% yield was obtained. With the increase of Lewis acidity of the catalyst, the yield of
CuF20TPP was up to 74%. As we all know, the product 1a was not observed in the absence of
catalysts (Table 1, entry 17). This indicated that CuTECP had much better catalytic performance.
With the above optimized conditions in hand, the effects of catalyst concentration, solvent effect,
reaction temperature, and cyclohexene concentration on the reaction results were investigated as
shown in Table S1. The yield elevated from 87% to 92% with the increasing amount of oxidant
from 1.5 to 3.0 equivalents. By screening common solvents for CDC reaction, we found that
benzene had the best solvent effect compared with acetonitrile, acetone, dichloroethane, and
chlorobenzene on catalyzing allyl esterification, and the highest yield was 92% with 0.1 mol%
catalysts in 24 h. Unfortunately, the yield decreased when the reaction was performed at 80 ℃,
and no significant improvement in the yield was observed at 120 ℃.
Under optimized reaction conditions (Table 1, entry 3), we subsequently explored the scope of
acids in the CuTECP-catalyzed CDC allylic esterification reaction. Both electron-donating and
-withdrawing aryl carboxylic acids reacted with cyclohexene and produced very good yields of the
products of allyl esterification, as shown in Table 2. When the benzoic acid bears
electron-donating groups, the yields were almost above 90% (2a-5a). The electron-withdrawing
substituents obviously lower the yields (6a-10a). The monosubstituted group had no obvious
effect on the yield of the corresponding products in ortho-position, meta-position, and
para-position (11a-13a), but when there were two substituted groups in the ortho-position, the
yield of allyl esterification decreased slightly (14a). In addition, the yield was 90% when the
substituents were cyano (16a). However, in the presence of phenolic hydroxyl groups, pyridyl
groups, or protected amino in the substrates, the esterification reaction could not proceed normally,
possibly due to the strong axial coordination of heteroatoms and CuTECP (15a, 17a, 22a, 24a).
Trans-cinnamic acid, 3-phenylpropanoic acid, and other aryl carboxylic acids such as 2-furoic acid
and 2-thiophene carboxylic acid afforded products of esterification in good yield (18a-21a, 23a).
Table 2
CuTECP-catalyzed CDC reaction of acids with cyclohexene. a

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a Reaction condition: benzoic acid (0.5 mmol), cyclohexene (5 mmol), catalyst CuTECP (0.1 mol%),
and benzene (1 mL) at 100 ℃ for 24 h. N.D. = not detected.
To further explore the potential of our methodology, the substrate scope of various alkenes was
explored, as shown in Table 3. The reaction of cyclopentene with 4-chlorobenzoic acid was
achieved to the corresponding esterification products (5aa) in 60% yield. Similarly, the
esterification products of expanded cyclic olefin substrate cycloheptene and cyclooctene were
obtained in good yields (5ba-5ca). Comparatively, the esterification yield of 4-methoxy benzoic
acid and cyclopentene was 94% (5fa). Notably, 2,3-dimethylbut-2-ene exhibited very high
selectivity, merely affording the mono-esterification product 5ga with a yield of 90%. Reactions of
asymmetric alkene such as hex-1-ene and hept-1-ene with acids proceeded smoothly with
regioselectivity of 5.7 to 1 and 6.1 to 1, respectively (5da-5db, 5ea-5eb). Interestingly, when

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2-methylbut-2-ene
reacted
with
4-methoxybenzoic
acid,
2-methylbut-2-en-1-yl
4-methoxybenzoate cis-trans isomers, and 3-methylbut-3-en-2-yl 4-methoxybenzoate were
afforded at a ratio of 1 to 1.15 (5ha-6ha). With decreasing C-H bond strength, esterification
products 5ja-5ma were not detected because of a large number of byproducts. When norbornene
was used as a substrate, esterification product 5ia was not produced after 24 h with a large amount
of benzoic acid remained. It is noteworthy, the reaction of hex-1-yne and 4-methoxy benzoic acid
produced 46% 11na and 53% 11nb (Scheme 2) [31]. In addition, a gram-level reaction experiment
was carried out for benzoic acid and cyclohexene CDC reaction: TON reached to 8100 with 0.01
mol% catalyst loading (Scheme 3).
Table 3.
Esterification of benzoic acid with various alkenes. a
a Reaction condition: benzoic acid (0.5 mmol), alkene (5 mmol), catalyst CuTECP (0.1 mol%), and
benzene (1 mL) at 100 ℃ for 24 h. N.D. = not detected.
Scheme 2. Propargylic esterification of 4-methoxy benzoic acid and hex-1-yne.

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Scheme 3. Gram-level reaction
Further experiments were conducted to elucidate the mechanism of the allylic esterification. The
reaction of sodium benzoate and cyclohexene did not result in the formation of allylic ester 2a
(Scheme S1), which indicated that the reaction of a carboxylate anion and allyl cation was not
involved in the allyl ester synthesis. When benzoyl peroxide was used as a substrate and oxidant
for the reaction, the reaction generated allyl esterification products in moderate yield (Scheme S2).
We succeeded to block this reaction by using radical scavengers butylated hydroxytoluene (BHT)
or 2,2,6,6-tetramethylpyridine N-oxide (TEMPO) (Scheme S3), suggesting that the oxidative
coupling reaction proceeded through the formation of an allylic radical intermediate.
Scheme 4. Proposed mechanism for allylic esterification.
In fact, the current reaction was found to follow Kharasch–Sosnovsky Reaction [32, 33].
According to the previous investigations on the mechanism of this reaction [34], there are three
pathways to generate the key high-valent allyl-copper intermediate, which will result in the release
of allylic ester: Beckwith–Zavitsas mechanism, Slough mechanism, and synergistic coordination
mechanism. As free radical scavengers could block the reaction effectively, synergistic
coordination mechanism may not play a key role in the present system. Suggested reaction
mechanism is depicted in Scheme 4. TECPCu(II) catalyzed the splitting of DTBP to generate
TECPCu(III)OtBu and tBuO free radical. TECPCu(III)OtBu then reacts with carboxylic acid to
produce TECPCu(III)O2CR, which will further turn into higher valent Cu(IV) intermediate A
through the Beckwith–Zavitsas or Slough pathway and finally release the target product to
complete the catalytic cycle. It should be pointed out that the reaction mechanism still needs more
investigations, and the capture of these transient high-valent copper porphyrin intermediate
species is a great challenge.
4. Conclusions

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In summary, a series of metal complexes (Mn, Fe, Co, Ni, Cu, Pd, and Ag) of TECP were
prepared and tested for the catalytic oxidative coupling of carboxylic acids and allylic sp3 C–H
bond for the synthesis of allylic esters. It was observed that CuTECP and FeTECP were effective
for this CDC reaction, while the other tested metal complexes of TECP were not effective.
Interestingly, in the gram-level test (0.01 mol% CuTECP catalyst loading at 100 ℃, with DTBP as
the oxidant), TON of the CDC reaction was up to 8100. The reaction proceeded smoothly with
highly broad substrate scope and good functional group tolerance comprising various carboxylic
acids, symmetric alkenes, asymmetric alkenes, and alkynes. In addition, the regioselective
esterification of asymmetric alkene was also explored. CuTECP-catalyzed oxidative esterification
of allylic C(sp3)-H bond and acid progressed by a radical mechanism. Further studies on metal
porphyrin-catalyzed asymmetric CDC reactions of C–O and C–C bond are currently underway in
our laboratory.
Acknowledgments
We gratefully acknowledge financial support from the National Natural Science Foundation of
China (No. 21671068).
Appendix A. Supplementary data
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1. Metalloporphyrin catalyzed cross dehydrogenative coupling reaction.
2. Esterification of allyl sp3 C–H bond with carboxylic acid using copper porphyrin.
3. Broad substrate scope and good functional group tolerance.
4. The best TON reached to 8100 with 81% yield under gram-level testing.