Cu(II)-catalyzed oxidative esterification of 2-carbonyl substituted phenols from the alcohol oxidation level

Article abstract of DOI:10.1016/j.tet.2013.08.079

A copper-catalyzed oxidative esterification of 2-carbonyl substituted phenols from the alcohol oxidation level is described. This protocol represents direct access to a range of 2-carbonylated aryl benzoate derivatives, which are important building blocks in the synthesis of natural and pharmacological compounds.

Full text of DOI:10.1016/j.tet.2013.08.079

Accepted Manuscript
Cu(II)-catalyzed oxidative esterification of 2-carbonyl substituted phenols from the
alcohol oxidation level
Satyasheel Sharma, Jihye Park, Mirim Kim, Jong Hwan Kwak, Young Hoon Jung, In
Su Kim
PII:
S0040-4020(13)01378-1
10.1016/j.tet.2013.08.079
TET 24768
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 23 July 2013
Revised Date: 26 August 2013
Accepted Date: 30 August 2013
Please cite this article as: Sharma S, Park J, Kim M, Kwak JH, Jung YH, Kim IS, Cu(II)-catalyzed
oxidative esterification of 2-carbonyl substituted phenols from the alcohol oxidation level, Tetrahedron
(2013), doi: 10.1016/j.tet.2013.08.079.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Cu(II)-catalyzed oxidative esterification of 2-carbonyl
substituted phenols from the alcohol oxidation level
Satyasheel Sharma, Jihye Park, Mirim Kim, Jong Hwan Kwak, Young Hoon Jung, and In
Su Kim*
School of Pharmacy, Sungkyunkwan University, Suwon 440-746, Republic of Korea
1

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Cu(II)-catalyzed oxidative esterification of 2-carbonyl substituted phenols
from the alcohol oxidation level
Satyasheel Sharma, Jihye Park, Mirim Kim, Jong Hwan Kwak, Young Hoon Jung, and In Su Kim*
School of Pharmacy, Sungkyunkwan University, Suwon 440-746, Republic of Korea
* Corresponding author. Tel.: +82-31-290-7788; fax: +82-31-292-8800; e-mail: insukim@skku.edu
Keywords: Alcohols; Aryl Benzoate; Cooper; Esterification; Phenols.
Abstract
A copper-catalyzed oxidative esterification of 2-carbonyl substituted phenols from the alcohol
oxidation level is described. This protocol represents direct access to a range of 2-carbonylated aryl
benzoate derivatives, which are important building blocks in the synthesis of natural and pharmacological
compounds.
1. Introduction
Esterification is one of the vital chemical reactions that have been extensively used in the chemical
and pharmaceutical industries.1 The general strategies usually involve the activation of the carboxylic
acid as an acyl halide, anhydride, or activated ester followed by nucleophilic substitution with alcohols.2
Although various research groups have exploited and developed several methods to the formation of
esters, oxidative esterification has received increasing attention from the atom economic point of view,
and has become an economical alternative to traditional ester formation. Recent efforts have been made
towards the oxidative coupling between aldehydes and alcohols.3 A variety of conditions have been
executed such as those using a stoichiometric oxidant, N-heterocyclic carbene activation, and transition
metal-mediated processes.4
An attractive alternative is the direct formation of esters from the alcohol oxidation level, which
represent a step forward toward green, economic, and sustainable processes. Alcohols are available at low
cost in great structural diversity, and are easy to handle and to store. Also, alcohols can be readily
oxidized into aldehydes under metal catalysis.5 Scheidt described a tandem oxidation of allylic and
benzylic alcohols to esters using N-heterocyclic carbenes as catalysts, which required large amounts of
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MnO2 as the oxidant.6 Very recently, Lei et al. developed a palladium-catalyzed aerobic esterification of
benzylic alcohols with methanol and long-chain aliphatic alcohols.7 Also, Beller and coworkers
developed a palladium/NHC-catalyzed oxidative esterification of benzylic alcohols.8 Though a significant
progress has been made toward oxidative processes for the formation of simple esters, no much attention
has been paid to the synthesis of aryl benzoate derivatives, which serve as an important building blocks in
the synthesis of natural and pharmacological compounds.9 Traditional methods for synthesizing these
compounds include esterification of phenols,10 trans-esterifications11 and Baeyer-Villiger oxidation
reactions.12 These reactions were often required strong acidic or basic conditions, which limit the scope of
functional groups. Recently, Chen13 and Pan14 described palladium/NHC and ruthenium/NHC-catalayzed
oxidative esterification of phenols with benzylic alcohols to afford aryl benzoate derivatives. However
there is no report for the oxidative esterification of 2-carbonyl substituted phenols from the alcohol
oxidation level. In particular, 2-carbonyl substituted aryl and alkylbenzoates are found to be important
precursor for biologically active moieties such as flavanols and benzopyrans.15
As part of an ongoing research program directed towards the development of transition metal-
catalyzed oxidative acylation reactions,16 we became interested in developing an efficient route to
synthesize 2-carbonyl substituted benzoates from the alcohol oxidation level. Herein we present the
copper-catalyzed esterification of 2-carbonyl substituted phenols with benzylic and aliphatic alcohols
using tert-butyl hydroperoxide (TBHP) as a convenient oxidant.
2. Results and discussion
Our investigation was initiated by reacting phenol derivative (1a) with benzyl alcohol (2a) and the
selected results are summarized in Table 1. To our delight, in the presence of 5 mol % of Cu(OAc)2ꢀH2O
o
and 4 equiv. of tert-butyl hydroperoxide (TBHP) in DCE at 80 C for 20 h, 1a can be coupled with 2a to
provide our desired ester 3a in 32% yield (Table 1, entry 1). Exclusion of either Cu(OAc)2ꢀH2O or TBHP
resulted in no observation of the desired product 3a. After screening of a range of copper catalysts,
Cu(OAc)2 was found to exhibit the highest reactivity (Table 1, entries 2–6). Further screening of solvents
under otherwise identical conditions revealed that DMSO was found to be the most effective solvent in
this coupling reaction, whereas other solvents such as DMF, MeCN, toluene, NMP and CH2Cl2 were less
effective (Table 1, entries 7–12). Intrestingly, this process provided the coupling product 3a under either
aqueous conditions or neat conditions, albeit in moderate yields (Table 1, entries 13 and 14). Screening of
oxidants showed that TBHP was superior to other oxidants such as K2S2O8, Ag2O and tert-butyl
peroxybenzoate (TBPB) (Table 1, entries 15–17). Decreasing amount of oxidant results in a slightly
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decreased reactivity (Table 1, entry 18).
Table 1. Selected optimization of reaction conditions.a
O
OH
OH
O
Cu catalyst
O
O
oxidant
solvent
80 oC, 20 h
1a
2a
3a
Entry
1
Catalyst
Cu(OAc)2·H2O
CuCl2·2H2O
Cu(OTf)2
CuI
Oxidant
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
K2S2O8
Ag2O
Solvent
DCE
Yield (%)b
32
2
DCE
20
3
DCE
trace
15
4
DCE
5
CuBr2
DCE
28
6
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
DCE
38
7
DMF
MeCN
toluene
NMP
CH2Cl2
DMSO
H2O
33
8
23
9
18
10
11
12
13
14
15
16
17c
trace
trace
70
56
44
DMSO
DMSO
DMSO
DMSO
trace
trace
30
TBPB
TBHP
18d
64
a
Reaction conditions: 1a (0.3 mmol), 2a (0.4 mmol), Cu catalyst (5 mol %), tert-butyl
o
b
hydroperoxide (TBHP, 70% in water) (4 equiv.), solvent (1 mL) at 80 C for 20 h in pressure tubes.
Isolated yield by flash column chromatography. c TBPB = tert-butyl peroxybenzoate. d TBHP (3 equiv.).
With the optimal reaction conditions in hand, a broad range of 2-carbonyl substituted phenols were
subjected to esterification with benzyl alcohol (2a), as shown in Table 2. The coupling of 2-
hydroxyacetophenones 1b–1e with electron-donating and withdrawing groups (OMe, Me, F and Br)
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underwent smoothly the esterification reaction to afford the corresponding products 3b–3e in moderate to
good yields. The yields were slightly increased when 2-hydroxybenzophenones 1f–1h were used instead
of 2-hydroxyacetophenones. Further investigation revealed that 2-hydroxybenzoates 1i–1l also provided
our desirable products in moderate yields. Various benzoates containing methyl, ethyl, phenyl and benzyl
were well tolerated under these conditions. In addition, ortho-hydroxy acetonaphthones 1m and 1n were
also found to undergo esterification. Further, we examined the effect of other directing groups instead of
carbonyl group at the ortho-position of phenol. Gratifingly, compound 1o with benzothiazole moiety
underwent esterification to give 3o in 57% yield.
Table 2. Scope of 2-carbonyl substituted phenolsa
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a
Reaction conditions: 1a–o (0.3 mmol), 2a (0.6 mmol), Cu(OAc)2 (5 mol %), TBHP (4 equiv.),
DMSO (1 mL) at 80 oC for 20 h. b Isolated yield by flash column chromatography.
Table 3. Scope of alcoholsa
a
Reaction conditions: 1a (0.3 mmol), 2b–l (0.6 mmol), Cu(OAc)2 (5 mol %), TBHP (4 equiv.),
DMSO (1 mL) at 80 oC for 20 h. b Isolated yield by flash column chromatography.
To further explore the substrate scope and limitations, a range of alcohol 2b–2l was screened to
couple with 2-hydroxyacetophenone (1a) under the optimal reaction conditions, as shown in Table 3. The
coupling of 1a and benzylic alcohols 2b–2g with electron-rich and electron-deficient groups (OMe, Me, F,
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Br and Cl), regardless of substituent position on the aromatic ring, was found to participate in the
acylation reaction to afford the corresponding products 4b–4g in moderate to good yields. However,
electron-withdrawing groups such as NO2 and COOMe at the para-position did not deliver the
corresponding ester products under the optimal reaction conditions. In addition, 2-naphthalenemethanol
(2h) smoothly underwent this coupling reaction to generate the product 4h in 58% yield. To our delight,
this reaction is not limited to benzylic alcohols. Aliphatic alcohols such as 1-hexanol, 1-butanol, 3-
phenylpropanol and cyclohexylmethanol also participated in the oxidative esterification as the acylating
agents to afford the corresponding products 4i–4l in moderate yields.
To examine the influence of ortho-carbonyl group of this process, competition experiment was
performed between 2-hydroxyacetophenone (1a) and phenol (1p) under the standard conditions (Scheme
1, eq. 1). Interestingly, no esterification of 1p was observed. In addition, we performed oxidative
benzoylation of 3-hydroxyacetophenone (1q) with 2a leading to no observation of the corresponding
product 3q under the standard conditions (Scheme 1, eq. 2). Thus, the lack of ester formation of phenols
1p and 1q suggest that the substrates binding to copper metal in a bidentate fashion could be one of the
key factors for the formation of ester.
Scheme 1. Mechanistic investigation.
A plausible reaction pathway is illustrated in Scheme 2. First, Cu(II) catalyst forms complex I with
2-hydroxyacetophenone (1a) and at the same time the alcohol 2a was oxidized to aldehyde by TBHP and
the t-BuO· radical reacts with TBHP to generate t-BuOO· radical,17 which can abstract H atom from the
aldehyde to give a reactive acyl radical.18 The newly formed benzoyl radical can react with complex I by
single electron transfer to produce Cu(III) complex II, which can undergo reductive elimination to afford
the product 3a and Cu(I) catalyst. Finally, Cu(I) catalyst is oxidized to Cu(II) by TBHP.19 Alternatively,
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Cu(II) complex I can undergo nucleophilic addition with aldehyde to deliver a copper hemiacetal
intermediate, which on further H-abstraction followed by a single electron transfer to lead the desired
product and Cu(I) catalyst.20
Scheme 2. Proposed mechanistic pathway.
3. Conclusion
In conclusion, we described a highly efficient method for the copper-catalyzed oxidative
esterification of 2-carbonyl substituted phenols from the alcohol oxidation level. These transformations
have been applied to a wide range of substrates. Also this protocol allows us to generate 2-carbonyl
substituted aryl and alkylbenzoates which constitute important functionallity for biologically active
moieties.
4. Experimental
4.1. General methods: Commercially available reagents were used without additional purification,
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unless otherwise stated. Sealed tubes (13 × 100 mm2) were purchased from Fischer Scientific and dried in
oven for overnight and cooled under a stream of nitrogen prior to use. Thin layer chromatography was
carried out using plates coated with Kieselgel 60F254 (Merck). For flash column chromatography, E.
Merck Kieselgel 60 (230-400 mesh) was used. Nuclear magnetic resonance spectra (1H and 13C NMR)
were recorded on a Bruker Unity 400 MHz and 700 MHz spectrometer for CDCl3 solutions and chemical
shifts are reported as parts per million (ppm) relative to, respectively, residual CHCl3 δH (7.24 ppm) and
CDCl3 δC (77.2 ppm) as internal standards. Resonance patterns are reported with the notations s (singlet),
d (doublet), t (triplet), q (quartet), and m (multiplet). In addition, the notation br is used to indicate a
broad signal. Coupling constants (J) are reported in hertz (Hz). IR spectra were recorded on a Varian 2000
Infrared spectrophotometer and are reported as cm-1. High-resolution mass spectra (HRMS) were
recorded on a JEOL JMS-600 spectrometer.
4.2. Typical procedure for the esterification of 2-carbonyl substtuted phenols: To an oven-dried
sealed tube charged with 2-hydroxyacetophenone (1a) (40.8 mg, 0.3 mmol, 1.0 equiv.), Cu(OAc)2 (2.7
mg, 0.015 mmol, 5 mol %), and TBHP (70% in water) (0.16 mL, 1.2 mmol, 4.0 equiv.) in DMSO (1 mL,
0.3 M) was added benzyl alcohol (2a) (65.4 mg, 0.6 mmol, 2 equiv.). The reaction mixture was allowed to
stir at 80 ºC for 20 h. After cooling at room temperature, the reaction mixture was evaporated onto silica
gel. Purification of the product by column chromatography (SiO2: n-hexanes/EtOAc = 40:1) provided 3a
(50.5 mg) in 70% yield
1
4.2.1. 2-Acetylphenyl benzoate (3a): yellow oil; Rf = 0.60 (n-hexanes/EtOAc = 6:1); H NMR (700
MHz, CDCl3) δ 8.20 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 7.7 Hz, 1H), 7.63 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.9
Hz, 1H), 7.51 (t, J = 7.9 Hz, 2H), 7.35 (t, J = 7.7 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 2.52 (s, 3H); 13C
NMR (175 MHz, CDCl3) δ 197.4, 165.1, 149.3, 133.7, 133.3, 131.2, 130.3, 129.1, 128.6, 126.1, 123.8,
29.7; IR (KBr) υ 2925, 1732, 1638, 1620, 1481, 1448, 1357, 1264, 1202, 1177, 1061, 956 cm-1; HRMS
(EI) Calcd for C15H12O3 [M]+ 240.0786, found 240.0785.
4.2.2. 2-Acetyl-5-methoxyphenyl benzoate (3b): colorless sticky solid; Rf = 0.40 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 8.19 (d, J = 8.2 Hz, 2H), 7.87 (d, J = 8.8 Hz, 1H), 7.61 (t, J = 7.5 Hz,
1H), 7.49 (t, J = 8.0 Hz, 2H), 6.84 (d, J = 8.8 Hz, 1H), 7.05 (s, 1H), 3.82 (s, 3H), 2.46 (s, 3H); 13C NMR
(175 MHz, CDCl3) δ 195.5, 165.0, 163.6, 151.5, 133.6, 132.3, 130.2, 129.2, 128.5, 123.3, 111.8, 109.1,
55.6, 29.3; IR (KBr) υ 2925, 1738, 1682, 1607, 1568, 1499, 1452, 1357, 1264, 1164, 1175, 1137, 1068,
1024, 964 cm-1; HRMS (EI) Calcd for C16H14O4 [M]+ 270.0892, found 270.0890.
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4.2.3. 2-Acetyl-5-methylphenyl benzoate (3c): yellow oil; Rf = 0.50 (n-hexanes/EtOAc = 6:1); 1H NMR
(700 MHz, CDCl3) δ 8.20 (d, J = 8.2 Hz, 2H), 7.77 (d, J = 8.0 Hz, 1H), 7.67 (t, J = 7.5 Hz, 1H), 7.50 (t, J
= 7.7 Hz, 2H), 7.15 (d, J = 8.0 Hz, 1H), 7.02 (s, 1H), 2.49 (s, 3H), 2.40 (s, 3H); 13C NMR (175 MHz,
CDCl3) δ 196.9, 165.2, 149.5, 144.8, 133.6, 130.4, 130.2, 129.3, 128.6, 128.2, 126.9, 124.3, 29.6, 21.3; IR
(KBr) υ 2923, 1738, 1682, 1615, 1451, 1357, 1266, 1229, 1143, 1062, 1024, 967 cm-1; HRMS (EI) Calcd
for C16H14O3 [M]+ 254.0943, found 254.0945.
1
4.2.4. 2-Acetyl-5-fluorophenyl benzoate (3d): colorless oil; Rf = 0.55 (n-hexanes/EtOAc = 6:1); H
NMR (700 MHz, CDCl3) δ 8.18 (d, J = 8.3 Hz, 2H), 7.89 (t, J = 7.7 Hz, 1H), 7.64 (t, J = 7.5 Hz, 1H),
7.51 (t, J = 8.1 Hz, 2H), 7.06–7.05 (m, 1H), 6.97 (d, J = 8.8 Hz, 1H), 2.50 (s, 3H); 13C NMR (175 MHz,
CDCl3) δ 195.8, 164.9 (d, JC–F = 255.9 Hz), 164.7, 151.1 (d, JC–F = 11.3 Hz), 134.0, 132.3 (d, JC–F = 10.5
Hz), 130.3, 128.8, 128.7, 127.6 (d, JC–F = 3.0 Hz), 113.4 (d, JC–F = 21.2 Hz), 111.8 (d, JC–F = 24.4 Hz),
29.7; IR (KBr) υ 2923, 1746, 1688, 1603, 1452, 1357, 1263, 1149, 1023, 976 cm-1; HRMS (EI) Calcd for
C15H11FO3 [M]+ 258.0692, found 258.0695.
4.2.5. 2-Acetyl-4-bromophenyl benzoate (3e): light yellow sticky solid; Rf = 0.50 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 8.17 (d, J = 8.3 Hz, 2H), 7.94 (s, 1H), 7.66–7.64 (m, 1H), 7.51 (t, J =
8.2 Hz, 2H), 7.11 (d, J = 8.5 Hz, 1H), 2.50 (s, 3H); 13C NMR (175 MHz, CDCl3) δ 196.0, 164.7, 148.2,
136.0, 134.0, 132.9, 132.8, 130.2, 128.7, 125.6, 119.3, 29.7; IR (KBr) υ 2917, 1742, 1694, 1600, 1472,
1356, 1260, 1202, 1055, 1023, 957 cm-1; HRMS (EI) Calcd for C15H11BrO3 [M]+ 317.9892, found
317.9890.
1
4.2.6. 2-Benzoylphenyl benzoate (3f): light yellow oil; Rf = 0.55 (n-hexanes/EtOAc = 6:1); H NMR
(700 MHz, CDCl3) δ 7.81 (d, J = 8.3 Hz, 2H), 7.77 (d, J = 8.3 Hz, 1H), 7.60–7.57 (m, 2H), 7.49 (t, J =
7.4 Hz, 1H), 7.44 (t, J = 7.4 Hz, 1H), 7.37–7.31 (m, 6H); 13C NMR (175 MHz, CDCl3) δ 194.7, 164.5,
148.7, 137.4, 133.4, 132.8, 132.1, 131.7, 130.3, 129.9, 129.6, 128.7, 128.3, 128.2, 125.7, 123.2; IR (KBr)
υ 2917, 1738, 1666, 1600, 1449, 1293, 1262, 1202, 1104, 1059, 1023, 928 cm-1; HRMS (EI) Calcd for
C20H14O3 [M]+ 302.0943, found 302.0940.
4.2.6. 2-Benzoyl-5-methoxyphenyl benzoate (3g): colorless sticky solid; Rf = 0.45 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 7.83 (d, J = 8.3 Hz, 2H), 7.72 (d, J = 8.2 Hz, 1H), 7.58 (d, J = 8.5 Hz,
1H), 7.50 (t, J = 7.5 Hz, 1H), 7.40 (t, J = 7.4 Hz, 1H), 7.34–7.31 (m, 4H), 6.87–6.85 (m, 2H), 3.85 (s,
3H); 13C NMR (175 MHz, CDCl3) δ 194.1, 164.5, 162.9, 150.8, 138.3, 133.4, 132.5, 132.3, 129.9, 129.4,
128.7, 128.2, 128.1, 123.9, 111.4, 108.8, 55.6; IR (KBr) υ 2932, 1738, 1660, 1608, 1448, 1317, 1272,
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1158, 1111, 1024, 949 cm-1; HRMS (EI) Calcd for C21H16O4 [M]+ 332.1049, found 332.1051.
4.2.7. 2-Benzoyl-5-chlorophenyl benzoate (3h): colorless sticky solid; Rf = 0.50 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 7.76 (t, J = 8.4 Hz, 4H), 7.75–7.73 (m, 2H), 7.51–7.44 (m, 2H), 7.36
(t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.6 Hz, 3H); 13C NMR (175 MHz, CDCl3) δ 193.3, 164.3, 147.1, 136.8,
133.6, 133.3, 133.2, 131.9, 131.3, 130.0, 129.9, 129.6, 128.5, 128.4, 128.3, 124.6; IR (KBr) υ 2923, 1745,
1668, 1598, 1472, 1398, 1260, 1205, 1177, 1113, 1055, 1023, 948 cm-1; HRMS (EI) Calcd for
C20H13ClO3 [M]+ 336.0553, found 336.0547.
1
4.2.8. Methyl 2-(benzoyloxy)benzoate (3i): light yellow oil; Rf = 0.48 (n-hexanes/EtOAc = 6:1); H
NMR (700 MHz, CDCl3) δ 8.20 (d, J = 8.2 Hz, 2H), 8.06 (d, J = 7.9 Hz, 1H), 7.63–7.58 (m, 2H), 7.50 (t,
J = 7.7 Hz, 2H), 7.34 (t, J = 7.7 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 3.72 (s, 3H); 13C NMR (175 MHz,
CDCl3) δ 165.3, 165.0, 150.7, 133.8, 133.5, 131.9, 130.2, 129.4, 128.5, 126.0, 123.9, 123.4, 52.1; IR
(KBr) υ 2953, 1731, 1606, 1451, 1299, 1265, 1205, 1126, 1082, 1061, 1024, 965 cm-1; HRMS (EI) Calcd
for C15H12O4 [M]+ 256.0736, found 256.0734.
4.2.9. Ethyl 2-(benzoyloxy)benzoate (3j): colorless sticky solid; Rf = 0.45 (n-hexanes/EtOAc = 6:1); 1H
NMR (700 MHz, CDCl3) δ 8.21 (d, J = 8.0 Hz, 2H), 8.07 (d, J = 7.9 Hz, 1H), 7.63–7.56 (m, 2H), 7.50 (t,
J = 7.9 Hz, 2H), 7.34 (t, J = 8.8 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 4.19 (q, J = 7.1 Hz, 2H), 1.07 (t, J =
7.0 Hz, 3H); 13C NMR (175 MHz, CDCl3) δ 165.2, 164.7, 150.5, 133.6, 133.5, 131.9, 130.2, 129.4, 128.5,
126.0, 123.9, 123.8, 61.1, 13.8; IR (KBr) υ 2982, 1742, 1720, 1606, 1451, 1295, 1266, 1204, 1125, 1061,
1023 cm-1; HRMS (EI) Calcd for C16H14O4 [M]+ 270.0892, found 270.0892.
4.2.10. Benzyl 2-(benzoyloxy)benzoate (3k): colorless sticky solid; Rf = 0.50 (n-hexanes/EtOAc = 6:1);
1H NMR (700 MHz, CDCl3) δ 8.12–8.09 (m, 3H), 7.60–7.58 (m, 2H), 7.44 (t, J = 8.2 Hz, 2H), 7.34 (t, J =
7.7 Hz, 1H), 7.22–7.20 (m, 6H), 5.18 (s, 2H); 13C NMR (175 MHz, CDCl3) δ 165.2, 164.5, 150.7, 135.2,
133.8, 133.4, 132.0, 130.2, 129.3, 128.5, 128.4, 128.3, 128.1, 126.0, 123.9, 123.6, 67.1; IR (KBr) υ 2923,
1739, 1731, 1606, 1451, 1291, 1266, 1204, 1122, 1078, 1061, 1023, 957 cm-1; HRMS (EI) Calcd for
C21H16O4 [M]+ 332.1049, found 332.1045.
o
4.2.11. Phenyl 2-(benzoyloxy)benzoate (3l): white solid; mp 68–71 C; Rf = 0.40 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 8.26 (d, J = 7.8 Hz, 1H), 8.20 (d, J = 8.2 Hz, 2H), 7.67 (t, J = 7.7 Hz,
1H), 7.57 (t, J = 7.5 Hz, 1H), 7.46–7.41 (m, 3H), 7.32–7.29 (m, 3H), 7.17 (t, J = 7.4 Hz, 1H), 7.07 (d, J =
8.4 Hz, 2H); 13C NMR (175 MHz, CDCl3) δ 165.2, 162.9, 151.1, 150.4, 134.4, 133.5, 132.2, 130.3, 129.3,
11

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129.2, 128.4, 126.2, 125.8, 124.1, 123.0, 121.5; IR (KBr) υ 2921, 1742, 1605, 1484, 1451, 1265, 1206,
1192, 1112, 1078, 1058, 1023 cm-1; HRMS (EI) Calcd for C20H14O4 [M]+ 318.0892, found 318.0883.
1
4.2.12. 2-Acetylnaphthalen-1-yl benzoate (3m): colorless oil; Rf = 0.45 (n-hexanes/EtOAc = 5:1); H
NMR (700 MHz, CDCl3) δ 8.33 (d, J = 8.4 Hz, 2H), 7.98 (d, J = 8.4 Hz, 1H), 7.89 (t, J = 8.6 Hz, 2H),
7.81 (d, J = 8.5 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.60–7.56 (m, 3H), 7.53–7.50 (m, 1H), 2.62 (s, 3H); 13C
NMR (175 MHz, CDCl3) δ 197.6, 165.0, 146.6, 136.3, 134.0, 130.4, 128.9, 128.8, 128.5, 127.9, 127.4,
127.3, 127.0, 126.1, 125.1, 122.9, 30.1; IR (KBr) υ 2917, 1742, 1683, 1626, 1598, 1451, 1358, 1259,
1177, 1082, 1068, 1021 cm-1; HRMS (EI) Calcd for C19H14O3 [M]+ 290.0943, found 290.0936.
4.2.13. 1-Acetylnaphthalen-2-yl benzoate (3n): light yellow sticky solid; Rf = 0.48 (n-hexanes/EtOAc =
5:1); 1H NMR (700 MHz, CDCl3) δ 8.20 (d, J = 8.3 Hz, 2H), 7.93 (d, J = 8.8 Hz, 1H), 7.89 (d, J = 7.9 Hz,
1H), 7.81 (d, J = 8.2 Hz, 1H), 7.65 (t, J = 8.4 Hz, 1H), 7.55–7.50 (m, 4H), 7.38 (d, J = 8.8 Hz, 1H), 2.60
(s, 3H); 13C NMR (175 MHz, CDCl3) δ 202.8, 164.8, 144.9, 134.0, 131.6, 130.9, 130.4, 130.3, 129.8,
128.8, 128.7, 128.4, 127.6, 126.1, 124.4, 121.4, 32.5; IR (KBr) υ 2922, 1739, 1702, 1595, 1491, 1351,
1260, 1208, 1177, 1080, 1062, 1022 cm-1; HRMS (EI) Calcd for C19H14O3 [M]+ 290.0943, found
290.0943.
4.2.14. 2-(Benzo[d]thiazol-2-yl)phenyl benzoate (3o): light yellow solid; mp 144–147 oC; Rf = 0.40 (n-
hexanes/EtOAc = 5:1); 1H NMR (700 MHz, CDCl3) δ 8.40 (d, J = 7.8 Hz, 1H), 8.31 (d, J = 8.2 Hz, 2H),
7.91 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.68 (t, J = 7.5 Hz, 1H), 7.56–7.53 (m, 3H), 7.44–7.40
(m, 2H), 7.33–7.31 (m, 2H); 13C NMR (175 MHz, CDCl3) δ 165.0, 162.2, 152.8, 148.5, 135.3, 133.7,
131.4, 130.6, 130.2, 129.4, 128.6, 126.4, 126.3, 126.1, 125.1, 123.8, 123.2, 121.3; IR (KBr) υ 2917, 1742,
1601, 1482, 1449, 1314, 1259, 1191, 1176, 1104, 1054, 1022, 966 cm-1; HRMS (EI) Calcd for
C20H13NO2S [M]+ 331.0667, found 331.0659.
4.2.15. 2-Acetylphenyl 4-methoxybenzoate (4b): colorless sticky solid; Rf = 0.45 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 8.14 (d, J = 8.8 Hz, 2H), 7.83 (d, J = 7.7 Hz, 1H), 7.54 (t, J = 7.7 Hz,
1H), 7.32 (t, J = 7.5 Hz, 1H), 7.19 (d, J = 8.0 Hz, 1H), 6.98 (d, J = 8.9 Hz, 2H), 3.87 (s, 3H), 2.51 (s, 3H);
13C NMR (175 MHz, CDCl3) δ 197.6, 164.7, 164.0, 149.4, 133.2, 132.4, 131.4, 130.0, 125.9, 123.9, 121.4,
113.9, 55.4, 29.8; IR (KBr) υ 2923, 1724, 1684, 1608, 1579, 1482, 1450, 1258, 1199, 1166, 1071, 1022,
963 cm-1; HRMS (EI) Calcd for C16H14O4 [M]+ 270.0892, found 270.0895.
4.2.16. 2-Acetylphenyl 4-fluorobenzoate (4c): yellow sticky solid; Rf = 0.55 (n-hexanes/EtOAc = 6:1);
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1H NMR (700 MHz, CDCl3) δ 8.22–8.20 (m, 2H), 7.84 (d, J = 7.8 Hz, 1H), 7.56 (t, J = 7.7 Hz, 1H), 7.35
(t, J = 7.5 Hz, 1H), 7.21–7.16 (m, 3H), 2.52 (s, 3H); 13C NMR (175 MHz, CDCl3) δ 197.4, 166.2 (d, JC–F
= 255.1 Hz), 164.1, 149.1, 133.4, 132.9 (d, JC–F = 9.6 Hz), 131.0, 130.3, 126.2, 125.5 (d, JC–F = 3.2 Hz),
123.8, 115.9 (d, JC–F = 22.1 Hz), 29.5; IR (KBr) υ 2924, 1739, 1688, 1630, 1507, 1448, 1357, 1265, 1199,
1154, 1069, 1013, 956 cm-1; HRMS (EI) Calcd for C15H11FO3 [M]+ 258.0692, found 258.0692.
4.2.17. 2-Acetylphenyl 4-bromobenzoate (4d): yellow solid; mp 121–124 oC; Rf = 0.50 (n-
hexanes/EtOAc = 6:1); 1H NMR (700 MHz, CDCl3) δ 8.05 (d, J = 8.6 Hz, 2H), 7.85 (d, J = 7.7 Hz, 1H),
7.65 (d, J = 8.6 Hz, 2H), 7.57 (t, J = 7.7 Hz, 1H), 7.36 (t, J = 7.7 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 2.51
(s, 3H); 13C NMR (175 MHz, CDCl3) δ 197.3, 164.5, 149.0, 133.4, 132.0, 131.7, 130.8, 130.3, 129.0,
128.2, 126.2, 123.8, 29.4; IR (KBr) υ 2917, 1739, 1687, 1603, 1589, 1486, 1357, 1264, 1199, 1173, 1071,
1010, 956 cm-1; HRMS (EI) Calcd for C15H11BrO3 [M]+ 317.9892, found 317.9888.
1
4.2.18. 2-Acetylphenyl 3-methylbenzoate (4e): colorless oil; Rf = 0.45 (n-hexanes/EtOAc = 6:1); H
NMR (700 MHz, CDCl3) δ 8.00–7.99 (m, 2H), 7.84 (d, J = 7.8 Hz, 1H), 7.56 (t, J = 7.9 Hz, 1H), 7.44–
7.43 (m, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.20 (d, J = 8.0 Hz, 1H), 2.52 (s, 3H), 2.43
(s, 3H); 13C NMR (175 MHz, CDCl3) δ 197.5, 165.2, 149.4, 138.5, 134.6, 133.3, 131.3, 130.7, 130.2,
129.1, 128.5, 127.4, 126.1, 123.8, 29.7, 21.2; IR (KBr) υ 2922, 1738, 1688, 1603, 1447, 1357, 1273, 1182,
1117, 1062, 956 cm-1; HRMS (EI) Calcd for C16H14O3 [M]+ 254.0943, found 254.0945.
4.2.19. 2-Acetylphenyl 2-naphthoate (4f): yellow oil; Rf = 0.40 (n-hexanes/EtOAc = 6:1); 1H NMR (700
MHz, CDCl3) δ 8.80 (s, 1H), 8.18 (d, J = 8.5 Hz, 1H), 7.98 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 8.5 Hz, 1H),
7.90 (d, J = 8.2 Hz, 1H), 7.86 (d, J = 7.8 Hz, 1H), 7.63–7.55 (m, 3H), 7.37 (t, J = 7.7 Hz, 1H), 7.27 (d, J =
8.0 Hz, 1H), 2.55 (s, 3H); 13C NMR (175 MHz, CDCl3) δ 197.5, 165.3, 149.4, 135.8, 133.4, 132.4, 132.1,
131.3, 130.2, 129.5, 128.7, 128.5, 127.8, 126.8, 126.3, 126.1, 125.3, 123.9, 29.7; IR (KBr) υ 2923, 1732,
1688, 1603, 1447, 1356, 1281, 1188, 1127, 1072, 950 cm-1; HRMS (EI) Calcd for C19H14O3 [M]+
290.0943, found 290.0936.
4.2.20. 2-Acetylphenyl 3-chlorobenzoate (4g): yellow oil; Rf = 0.48 (n-hexanes/EtOAc = 6:1); 1H NMR
(700 MHz, CDCl3) δ 8.16 (s, 1H), 8.07 (d, J = 7.7 Hz, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.60–7.56 (m, 2H),
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7.45 (t, J = 7.9 Hz, 1H), 7.37 (t, J = 7.7 Hz, 1H), 7.20 (d, J = 8.0 Hz, 1H), 2.52 (s, 3H); C NMR (175
MHz, CDCl3) δ 197.3, 164.0, 149.0, 134.8, 133.7, 133.5, 131.0, 130.8, 130.4, 130.2, 129.9, 128.3, 126.3,
123.8, 29.4; IR (KBr) υ 2924, 1742, 1687, 1604, 1576, 1447, 1357, 1282, 1249, 1199, 1118, 1071, 957
cm-1; HRMS (EI) Calcd for C15H11ClO3 [M]+ 274.0397, found 274.0394.
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4.2.21. 2-Acetylphenyl 2-fluorobenzoate (4h): yellow sticky solid; Rf = 0.50 (n-hexanes/EtOAc = 6:1);
1H NMR (700 MHz, CDCl3) δ 8.13 (t, J = 7.7 Hz, 1H), 7.85 (d, J = 7.8 Hz, 1H), 7.58–7.55 (m, 2H), 7.35
(t, J = 7.6 Hz, 1H), 7.27 (t, J = 7.7 Hz, 1H), 7.23–7.18 (m, 2H), 2.54 (s, 3H); 13C NMR (175 MHz,
CDCl3) δ 197.3, 162.6 (d, JC–F = 3.3 Hz), 162.3 (d, JC–F = 261.5 Hz), 148.9, 135.4 (d, JC–F = 9.4 Hz),
133.4, 132.7, 130.9, 130.3, 126.2, 124.2 (d, JC–F = 3.9 Hz), 123.9, 117.8 (d, JC–F = 9.3 Hz), 117.2 (d, JC–F
= 22.0 Hz) 24.9; IR (KBr) υ 2917, 1748, 1686, 1613, 1488, 1448, 1357, 1291, 1243, 1197, 1126, 1052,
954 cm-1; HRMS (EI) Calcd for C15H11FO3 [M]+ 258.0692, found 258.0690.
4.2.22. 2-Acetylphenyl hexanoate (4i): colorless oil; Rf = 0.44 (n-hexanes/EtOAc = 6:1); 1H NMR (700
MHz, CDCl3) δ 7.77 (d, J = 7.7 Hz, 1H), 7.50 (t, J = 8.4 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.08 (d, J = 8.1
Hz, 1H), 2.59 (t, J = 7.5 Hz, 2H), 2.52 (s, 3H), 1.73–1.78 (m, 2H), 1.39–1.35 (m, 4H), 0.90 (t, J = 7.0 Hz,
3H); 13C NMR (175 MHz, CDCl3) δ 197.6, 172.2, 149.0, 133.2, 130.9, 130.1, 125.8, 123.7, 34.2, 31.2,
29.4, 24.1, 22.3, 13.8; IR (KBr) υ 2931, 1765, 1689, 1604, 1448, 1357, 1250, 1201, 1138, 1098, 956 cm-1;
HRMS (EI) Calcd for C14H18O3 [M]+ 234.1256, found 234.1255.
1
4.2.23. 2-Acetylphenyl butyrate (4j): colorless oil; Rf = 0.55 (n-hexanes/EtOAc = 6:1); H NMR (700
MHz, CDCl3) δ 7.76 (d, J = 7.7 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H), 7.29 (t, J = 7.7 Hz, 1H), 7.08 (d, J = 8.0
Hz, 1H), 2.57 (t, J = 7.4 Hz, 2H), 2.52 (s, 3H), 1.76–1.80 (m, 2H), 1.02 (t, J = 7.4 Hz, 3H); 13C NMR
(175 MHz, CDCl3) δ 197.6, 172.0, 149.0, 133.3, 130.9, 130.1, 125.8, 123.7, 36.1, 29.4, 18.0, 13.6; IR
(KBr) υ 2968, 1760, 1694, 1630, 1447, 1358, 1282, 1251, 1140, 1072, 956 cm-1; HRMS (EI) Calcd for
C12H14O3 [M]+ 206.0943, found 206.0942.
4.2.24. 2-Acetylphenyl 3-phenylpropanoate (4k): colorless sticky solid; Rf = 0.40 (n-hexanes/EtOAc =
6:1); 1H NMR (700 MHz, CDCl3) δ 7.78 (d, J = 7.7 Hz, 1H), 7.50 (t, J = 7.8 Hz, 1H), 7.31–7.28 (m, 3H),
7.27–7.25 (m, 2H), 7.21 (t, J = 7.7 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H), 3.08 (t, J = 7.5 Hz, 2H), 2.94 (t, J =
7.5 Hz, 2H), 2.48 (s, 3H); 13C NMR (175 MHz, CDCl3) δ 197.5, 171.3, 148.9, 140.1, 133.3, 130.7, 130.2,
128.5, 128.3, 126.3, 126.0, 123.7, 35.9, 30.5, 29.3; IR (KBr) υ 2925, 1760, 1688, 1603, 1448, 1357, 1283,
1251, 1198, 1129, 1072, 956 cm-1; HRMS (EI) Calcd for C17H16O3 [M]+ 268.1099, found 268.1106.
4.2.25. 2-Acetylphenyl cyclohexanecarboxylate (4l): colorless oil; Rf = 0.50 (n-hexanes/EtOAc = 6:1);
1H NMR (700 MHz, CDCl3) δ 7.75 (d, J = 7.7 Hz, 1H), 7.49 (t, J = 7.7 Hz, 1H), 7.28 (t, J = 7.7 Hz, 1H),
7.05 (d, J = 8.1 Hz, 1H), 2.52 (s, 3H), 2.10–2.08 (m, 2H), 1.82–1.79 (m, 2H), 1.68–1.66 (m, 1H), 1.58–
1.54 (m, 2H), 1.36–1.23 (m, 4H); 13C NMR (175 MHz, CDCl3) δ 197.8, 174.3, 149.1, 133.2, 131.2, 129.9,
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125.8, 123.7, 43.2, 29.5, 28.7, 25.6, 25.3; IR (KBr) υ 2932, 1756, 1689, 1603, 1482, 1448, 1356, 1283,
1250, 1190, 1149, 1116, 1015, 956 cm-1; HRMS (EI) Calcd for C15H18O3 [M]+ 246.1256, found 246.1254..
Acknowledgment
This research was supported by Basic Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No.
2013R1A2A2A01005249).
Supplementary data
1
Supplementary data available: H NMR and 13C NMR copies of all compounds. Supplementary data
associated with this article can be found in the online version, at http://
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Supplementary Data
Cu(II)-catalyzed oxidative esterification of 2-carbonyl
substituted phenols from the alcohol oxidation level
Satyasheel Sharma, Jihye Park, Mirim Kim, Jong Hwan Kwak,
Young Hoon Jung, and In Su Kim*
School of Pharmacy, Sungkyunkwan University, Suwon 440-746, Republic of Korea
* Corresponding authors. Tel.: +82-31-290-7788; fax: +82-31-292-8800; e-mail: insukim@skku.edu
List of the Contents
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