Fe-Catalyzed Aerobic Oxidative C-CN Bond Cleavage of Arylacetonitriles Leading to Various Esters

Article abstract of DOI:10.1021/acs.joc.6b01594

Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri alkoxsilanes, silicate esters, or borate esters have been developed. The acyl groups which were in situ generated via chemoselective C(CO)-CN bond cleavage were directly used as electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant O₂ feature this transformation and make it a practical and sustainable protocol to afford esters.

Full text of DOI:10.1021/acs.joc.6b01594

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Article
Fe-catalyzed Aerobic Oxidative C-CN Bond Cleavage
of Arylacetonitriles Leading to Various Esters
Weiguang Kong, Bingnan Li, Xuezhao Xu, and Qiuling Song
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01594 • Publication Date (Web): 24 Aug 2016
Downloaded from http://pubs.acs.org on August 24, 2016
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Fe-catalyzed Aerobic Oxidative C-CN Bond Cleavage of
Arylacetonitriles Leading to Various Esters
Weiguang Kong,† Bingnan Li,† Xuezhao Xu,†and Qiuling Song*,†,‡
†Institute of Next Generation Matter Transformation, College of Chemical Engineering,
College of Materials Science & Engineering at Huaqiao University, 668 Jimei Blvd, Xiamen,
Fujian, 361021, P. R. China.
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‡ Beijing National Laboratory for Molecular Sciences, Beijing, 100190, China
Fax: 86ꢀ592ꢀ6162990; email: qsong@hqu.edu.cn
Abstract：
Feꢀcatalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri
alkoxsilanes, silicate esters or borate esters have been developed. The acyl groups which were
inꢀsitu generated via chemoselective C(CO)ꢀCN bond cleavage were directly used as
electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular
oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and
reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting
materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant
O2 feature this transformation and makes it a practical and sustainable protocol to afford
esters.
Introduction
Despite the high bond dissociation energy of C−CN bond (>100 kcal/mol), direct
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cleavage of a CꢀCN bond has still attracted great attention and becomes an appealing area in
modern synthetic chemistry due to its enormous potential in construction of complex
moleculars.1 Numerous transition metals, such as Ni,2 Pd,3 Rh4 and Cu5 have been extensively
explored to either mediate or catalyze this transformation. Oxidative addition mechanism has
successfully explained vast majority of reported CꢀCN bond cleavage reactions.6 However, to
the best of our knowledge, only few examples reported the CꢀCN bond cleavage not via
oxidative addition mechanism.7 As one of the most abundant and inexpensive transition metal
salts, Fe salts are used as a catalyst for the transformations which possess both industrial
significance and academic importance.8 The ꢀCOOR moiety is a key structural motif in both
natural and synthetic organic compounds, therefore various methods have been developed for
the construction of esters,9 including the acylation of alcohols and phenols. However, long
duration, harsh reaction conditions (strong basic or acidic environment and anhydrous
conditions) are needed when anhydrides or acyl chlorides were employed which extremely
limit the functional groups tolerability, especially for phenols.10 We envisioned that
phenylacetonitrile has a great chance to be a cheap and readily available starting material for
the synthesis of esters since CN group is detachable via a chemoselective cleavage of
C(CO)ꢀCN bond. For instance, Yu and his coworkers firstly reported a novel CꢀCN bond
cleavage reaction in arylacetonitriles to afford aryl carboxylic esters by using Samarium as
catalyst in oneꢀpot process.11 After that, iodine was used as a catalyst for this conversion
reported later by the same authors as part of their continuation of these studies.12 However,
their transformations are greatly restricted due to the dependence on strong
electronꢀwithdrawing substituents on the aromatic rings (such as the nitro group) (Scheme 1a).
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Therefore, it still needs a great breakthrough to establish a general, simple, and efficient
method by using a variety of arylacetonitriles to lead to various esters.
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Scheme 1. Ester Formation via Oxidative Decyanation of Arylacetonitriles
As one of our continuous interest on transitionꢀmetalꢀcatalyzed aerobic oxidation
reaction,13 herein we would like to report an Feꢀcatalyzed aerobic oxidative esterification of
arylacetonitriles with alcohols, or silicate esters and boric acid esters as alcohols surrogates.
Esters were formed with molecular oxygen as the terminal oxidant in good to excellent yields
with broad substrate scope (Scheme 1b).
Results and Discussion
Arylacetonitrile (1a) and nꢀbutanol (2a) were selected as substrates in model reactions to
probe the feasibility of the reaction between arylacetonitriles and alcohols. Based on our
previous research, we initiated our study in the presence of FeCl3 and pyridine in toluene at
O
120 C under O2. To our delight, the desired product 3aa was formed in 40% yield. Further
catalyst screening indicated that FeBr3 showed the best catalytic reactivity among FeCl3,
Fe(OAc)2, FeBr2, FeBr3, Fe(ClO4)3, Fe(OH)3 and Fe2O3 (Table 1, entries 1ꢀ4 and Table S1 in
Supporting Information). When other bases, such as thiazole and Et3N were added to the
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reaction, the desired product was obtained in very low yield (Table 1, entries 5ꢀ6, Table S2,
Supporting Information), suggesting that pyridine might be irreplaceable for this reaction. The
role of pyridine was not clear right now, it might acted as ligand involving in the reaction or
help the leaving of proton on αꢀC of benzylnitriles to form the benzoyl cyanide intermediate.
Solvents screening indicated that PhCl is the superior choice over toluene, DMF, DMSO,
mꢀxylene, DME, NMP and dioxane (Table 1, entries 7ꢀ8, Table S3, Supporting Information).
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O
When temperature was increased to 130 C, the yield increased from 75% to 98%; however,
lowering the temperature to 110 OC or 100 OC only dramatically reduced the yields of desired
product 3aa (Table 1, entries 7ꢀ10). If the reactions were conducted under N2 and air
atmosphere, very low amount of product were detected (Table 1, entries 12ꢀ13). Eventually
fine tuning on catalyst and ligand loadings revealed that the optimized reaction condition for
3aa was: arylacetonitrile 1a (0.5 mmol), alcohol 2a (1.5 mmol), FeBr3 (10 mol%), pyridine
(0.5 equiv), PhCl (1 mL) at 130 oC under oxygen (Table 1, entry 10).
Table 1. Optimization of the Reaction Conditions.a
O
catalyst/ligand
nBuOH
CN
OnBu
+
additive, solvent, temp.
O2, 5 h
1a
2a
3aa
Entry
1
Catalyst
(mol%)
Ligand
(equiv)
Solvent
toluene
Temp (oC) Yield of 3aa
(%)b
FeCl3 (10)
pyridine (0.5)
120
40
Fe(OAc)2 (10)
FeBr2 (10)
2
3
pyridine (0.5)
pyridine (0.5)
toluene
toluene
120
120
trace
28
4
5
6
7
FeBr3 (10)
FeBr3 (10)
FeBr3 (10)
FeBr3 (10)
pyridine (0.5)
thiazole (0.5)
Et3N (0.5)
toluene
toluene
toluene
PhCl
120
120
120
120
62
trace
trace
75
pyridine (0.5)
8
9
FeBr3 (10)
FeBr3 (10)
pyridine (0.5)
pyridine (0.5)
PhCl
PhCl
100
110
10
25
10
FeBr3 (10)
FeBr3 (5)
FeBr3 (10)
FeBr3 (10)
-
pyridine (0.5)
pyridine (0.5)
pyridine (0.5)
pyridine (0.5)
pyridine (0.5)
-
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
130
130
130
130
130
130
98 (90)
58
11
12c
13d
14
trace (N2)
10 (air)
trace
15
FeBr3 (10)
12
a
Conditions: 1a (0.5 mmol), 2a (1.5 mmol), catalyst, solvent (2 mL), temp., under O2 in a sealed tube.
b
GC yield, the yield was listed in the parenthesis. c Under N2. d Under air.
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With the optimal reaction conditions available, the protocol was extended to different
arylacetonitriles. The results were shown in table 2. The aerobic oxidative esterification of
arylacetonitriles proceeded in good to excellent yields regardless of the electronic nature of
the substituents on the aromatic rings: both electronꢀwithdrawing (ꢀCl, ꢀBr, ꢀF, ꢀNO2) and
electronꢀdonating (ꢀCH3, ꢀOCH3) groups at the 4ꢀ, 3ꢀand 2ꢀpositions are good substituents for
this transformation (Table 2, entries 3ba-3oa). Moreover, a variety of functional groups, such
as trifluoromethyl, alkynyl and cyano groups were all tolerable in this reaction (Table 2,
entries 3pa-3ra). In addition, 2ꢀnaphthyl was compatible in this reaction as well to give the
corresponding product 3sa in 71% yield (Table 2, 3sa).
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Table 2. Substrate Scope for the formation of Esters from Arylacetonitriles 1 and nꢀBuOH 2a.
The scope of alcohols for this transformation was further investigated. As shown in Table
3, both phenylmethanol and 2ꢀphenylethanol were tolerated in this esterification in spite of
the types of electronic variations and positions of substituents on the aromatic rings (Table 3,
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3ab-3ah). Remarkably, heteroaromatic ethanols, such as 2ꢀthiophene ethanol and 3ꢀthiophene
ethanol, also rendered the desired esters in fair to good yields (Table 3, 3ai and 3aj).
Significantly, pꢀsubstituted phenols and 2, 3, 4, 5, 6ꢀpentafluorophenol which have special
biological activities were also tolerable under the optimal reaction conditions to afford
corresponding products (Table 3, 3al-3an, 3ao), which are the first cases in similar reports.
Both primary and secondary aliphatic alcohol, including some natural alcohols, which are
susceptible to oxidative conditions, survived well under this reaction system, generating
desired products in good yields (Table 3, 3aa, 3ak, 3ap ꢀ 3ar). Intriguingly, the wellꢀknown
cholesterol was tolerated in this condition, 3as was afforded in 46% yield in 20 h, fuether
extension of the reaction time didn’t improve its yield, probably due to the decomposition of
cholesterol in the system. The success of cholesterol indicated the feasibility of using this
method to achieve lateꢀstage complex compound transformation.
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Table 3. Alcohol Scope for the Formation of Esters from Phenylacetonitrile (1a) and alcohols
2.
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It is worth to note that when MeOH was employed under the standard conditions, only
28% yield of desired product was obtained, suggesting that methyl ester will be a hurdle and
limitation for this transformation. In order to find the key to the problem and further verify the
compatibility of this system, we investigated other substrates which might be the potential
MeOH surrogates. And trimethyl borate 4, tetramethyl silicate 5 and trimethoxysilane 6
caught our eyes. To our most delight, application of the above protocol to 4, 5 and 6 didn’t
encounter any problems and the corresponding desired methyl esters were formed in good to
excellent yields (Table 4, 3at, 3’at and 3lt-3’tt). Furthermore, Good to excellent yields was
also achieved with silicate esters such as tetraethyl orthosilicate and tetrapropoxysilane and
borate esters such as triethyl borate and tripropyl borate. (Table 4, 3ak, 3’ak, 3au, 3’au). The
excellent reactivity of these three types of compounds further demonstrates the strong
compatibility of this system.
Table 4. Substrate Scope for the Formation of Esters from Arylacetonitriles 1 and Borate
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esters, Silicate esters or Trimethoxysilane.
5
6
7
8
O
4
5
6
B(OMe)3
3u
FeBr3 (10 mol%)
pyridine
CN
O
R
Si(OMe)4
Si(OMe)3H
R
3'u
3''u
PhCl, O2, 130 o
C
1
9
O
O
O
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O
b
c
O
b
3at
91%
O
3ak
88%
83%
3au
90%
O
O
c
3'at
89%
3'ak
3'au
82%
O
3ot
90%
O
O
O
3lt
3ft
89%
76%
3'ot
3"ot
78%
84%
3'lt
3'ft
82%
76% O2N
Cl
O
O
O
3nt
74%
O
3'nt
72%
80%
O
3' tt 88%
NO2
3"nt
a
1
4, 5
6
or (1.5 mmol), FeBr3 (10 mol %),
Reaction conditions: Phenylacetonitrile ( ) (0.5 mmol),
pyridine (0.5 equiv), PhCl (2 mL) in O2 in a sealed tube, O2, 130 oC, 9 h.b triethyl borate and tripropyl
borate were used. c tetraethyl orthosilicate and tetrapropoxysilane were used.
Gratifyingly, the reaction could be readily scaled up to gram scale (8 mmol) without
deteriorating its efficiency (Table 5).
Table 5. Scaleꢀup Reaction.
We further performed several control experiments under the standard conditions in order
to probe the reaction mechanism of the ester formation. Radical trapping experiments were
firstly conducted by adding 2, 2, 6, 6ꢀtetramethylꢀ1ꢀpiperidinyloxy (TEMPO) and BHT into
the standard conditions of arylacetonitrile (1a) and nꢀBuOH (2a). As shown in Scheme 2, the
reaction was totally inhibited by TEMPO; with BHT as a radical trapper, the yield was
decreased to 8%. The results suggested that a radical pathway should be involved in this
reaction [Scheme 2, eq. (1)]. The reaction between benzoyl cyanide 7 with nꢀBuOH under the
standard conditions was also investigated and the desired product was afforded in 97% yield
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[Scheme 2, eq. (2)]. Combining with the previous report, this result demonstrated that benzoyl
cyanide 7 might be the key intermediate in the transformation.
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9
To understand the origin of the oxygen in the new carbonyl group of the desired product,
isotope labeled reactions were conducted under standard conditions with 18O2, GCMS and
HRMS spectra showed that 93% 16O18Oꢀ3aa was obtained [Scheme 2, eq.(3), Scheme S1,
Supporting Information]. With the addition of 3 equivalent of H2O under 18O2, 92% of
product was the one which contains 18O [Scheme 2, eq. (4)]. With the addition of 3 equivalent
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of H2 O under 16O2, 98% of product was the one which only contains 16O [Scheme 2, eq. (5)].
These three isotope labeling experiments clearly demonstrated that the oxygen was from
18
molecular dioxygen, not from water, since one equivalent H2 O should be obtained under
18O2, if the oxygen was from water, unlabeled product 16O16Oꢀ3aa should be the major one
under 18O2/H2O (3 equiv.) system, since H2O is three time than H2 O. In addition, eq. (5)
18
suggested that the incorporation of the label was not from the exchange with water since
almost no 18O was incorporated into the product under 16O2/H218O (3 equiv.) system.
Therefore, we have reason to believe that the oxygen atom in the new carbonyl group of the
desired product was from dioxygen.
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O
radical scavenger (3 equiv)
the standard condition
nBuOH
CN
OBun
+
(1)
5
6
3aa
TEMPO,
, trace
1a
2a
3aa
BHT,
, 9%
7
8
O
O
the standard condition
OBun
, 97%
nBuOH
+
(2)
(3)
CN
9
7
2a
3aa
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O
the standard condition
18O2
OBun
nBuOH
CN
+
+
2a
18O16O-3aa: 16O16O-3aa = 93:7, 94%
1a
O
the standard condition
18O2, H216O (3 equiv)
OBun
nBuOH
CN
O
(4)
1a
18O16
O
O16
O
-3aa =
92:8, 87%
(5)
2a
-3aa: 16
O
the standard condition
16O2/H218O (3 equiv)
OBun
OBun
3a
18O16O-3aa: 16O16O-3aa = 2:98, 96%
Scheme 2. Control Experiments under the Standard Conditions
On the basis of the control experiments, we proposed a plausible mechanism for the
reaction (Scheme 3): arylacetonitrile is oxidized into benzoyl cyanide 7 by oxygen, which is
further attacked by alcohols or alcohols surrogates (borate esters, silicate esters or
trimethoxysilane) to lead to intermediate 8, in which the cleavage of CꢀCN bond occurred
under the optimal conditions to generate desired product 3.
Scheme 3. Proposed Mechanism
Conclusions
In conclusion, an Feꢀcatalyzed aerobic oxidative esterifications of arylacetonitriles with
various alcohols has been disclosed. Complex alcohols are competent candidates in this
transformation and most of the corresponding desired products are obtained in good to
excellent yields When MeOH was used, methyl benzoate are obtained with relatively lower
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yields probably due to the low boiling point of MeOH. However, trimethyl borate, tetramethyl
silicate and trimethoxysilane have been found to be excellent MeOH surrogates and showed
great compatibility in this transformation as well. Other silicate esters or borate esters are also
suitable for this reaction. Corresponding esters could be obtained in good to excellent yields
with a very broad range of substrate scope. These protocols feature in readily accessible
starting materials, inexpensive and abundant catalyst, molecular oxygen as the sole oxidant
and excellent functional group tolerance. Further investigation on synthetic application and
the mechanism of this reaction will be reported in due course.
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EXPERIMENTAL SECTION
General information. All experiments were conducted with a sealed pressure vessel.
1
Flash column chromatography was performed over silica gel (200ꢀ300 mesh). H NMR
spectra were recorded on a 500 MHz spectrometers. Chemical shifts (in ppm) were referenced
to CDCl3 (δ = 7.26 ppm) as an internal standard. 13C NMR spectra were obtained by using the
same NMR spectrometers and were calibrated with CDCl3 (δ = 77.00 ppm). Unless otherwise
noted, materials obtained from commercial suppliers were used without further purification.
Procedure and characterization data for products
Butyl benzoate (3aa CAS: 136ꢀ60ꢀ7).13d A sealed pressure vessel was charged with FeBr3
(14.0 mg, 0.05 mmol), phenylacetonitrile (58.5 mg, 0.5 mmol), nꢀbutyl alcohol (111.2 mg, 1.5
mmol), pyridine (19.8 mg, 0.25 mmol), and chlorobenzene (1 mL). The resulting solution was
o
stirred at 130 C under O2 (monitored by TLC and GC) for 5 hours. Upon completion of the
reaction, ethyl acetate (20 mL) was added, the green layer were washed with brine (20 mL)
twice, the combined aqueous layers was extracted with ethyl acetate (20 mL) twice. The
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combine organic layers were dried over anhydrous Na2SO4. The solvents were removed via
rotary evaporator and the residue was purified with flash chromatography (silica gel, ethyl
acetate: petroleum ether = 60:1) to give 81 mg of the product in 90% yield as a light yellow
oil. 1H NMR (500 MHz, CDCl3) δ 8.05 (dd, J = 8.3, 1.3 Hz, 2H), 7.57 – 7.49 (m, 1H), 7.47 –
7.40 (m, 2H), 1.75 (dd, J = 14.8, 6.9 Hz, 2H), 1.52 – 1.44 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H).
13C{1H} NMR (125 MHz, CDCl3) δ 166.6, 132.7, 130.5, 129.5, 128.2, 64.8, 30.7, 19.2, 13.7.
Butyl 2ꢀfluorobenzoate (3ba CAS: 371779ꢀ67ꢀ8).14 The same procedure was used for
2ꢀ(2ꢀfluorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 73.4 mg of the product in 75% as
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a light yellow solid. H NMR (500 MHz, CDCl3) δ 7.92 (m, 1H), 7.53 – 7.46 (m, 1H), 7.19
(td, J = 7.7, 1.0 Hz, 1H), 7.12 (m, 1H), 4.33 (t, J = 6.6 Hz, 2H), 1.74 (dd, J = 14.8, 6.9 Hz,
2H), 1.48 (dt, J = 15.0, 7.4 Hz, 2H), 0.97 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (125 MHz,
CDCl3) δ 164.5 (d, J = 3.7 Hz), 161.9 (d, J = 259.8 Hz), 134.3 (d, J = 8.9 Hz), 132.0 (d, J =
0.6 Hz), 123.9 (d, J = 3.9 Hz), 119.1 (d, J = 9.9 Hz), 116.9 (d, J = 22.5 Hz), 65.2, 30.7, 19.2,
13.7.
Butyl 4ꢀfluorobenzoate (3ca CAS: 3888ꢀ64ꢀ0).15 The same procedure was used for
2ꢀ(4ꢀfluorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 79.4 mg of the product in 81% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.15 – 7.84 (m, 2H), 7.14 – 7.07 (m,
2H), 4.31 (t, J = 6.6 Hz, 2H), 1.77 – 1.71 (m, 2H), 1.48 (dt, J = 9.2, 7.4 Hz, 2H), 0.98 (t, J =
7.4 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 165.7 (s), 165.7(d, J = 254.5 Hz), 132.0 (d,
J = 9.3 Hz), 126.8 (d, J = 3.0 Hz), 115.4 (d, J = 21.9 Hz), 65.0 , 30.8, 19.3, 13.8.
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Butyl 2ꢀchlorobenzoate (3da CAS: 52468ꢀ48ꢀ1).16 The same procedure was used for
2ꢀ(2ꢀchlorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 79.5 mg of the product in 75% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 7.81 (dd, J = 7.8, 1.6 Hz, 1H), 7.42 (m,
2H), 7.30 (m, 1H), 4.34 (t, J = 6.6 Hz, 2H), 1.78 – 1.72 (m, 2H), 1.49 (m, 2H), 0.97 (t, J = 7.4
Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 165.9, 133.6, 132.4, 131.3, 131.0, 130.5, 126.5,
65.5, 30.7, 19.3, 13.7.
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Butyl 3ꢀchlorobenzoate (3ea CAS: 63987ꢀ54ꢀ2).14 The same procedure was used for
2ꢀ(3ꢀchlorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 84.8 mg of the product in 80% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.01 (t, J = 1.8 Hz, 1H), 7.95 – 7.90
(m, 1H), 7.52 (m, 1H), 7.38 (t, J = 7.9 Hz, 1H), 4.33 (t, J = 6.6 Hz, 2H), 1.76 (dd, J = 14.5,
7.2 Hz, 2H), 1.50 – 1.45 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3)
δ 165.5, 134.5, 132.8, 132.5, 129.6, 129.6, 127.6, 65.2, 30.7, 19.2, 13.7.
Butyl 4ꢀchlorobenzoate (3fa CAS: 27942ꢀ64ꢀ9).14 The same procedure was used for
2ꢀ(4ꢀchlorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 85.9 mg of the product in 81% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.02 – 7.92 (m, 2H), 7.46 – 7.36 (m,
2H), 4.32 (t, J = 6.6 Hz, 2H), 1.75 (dt, J = 14.5, 6.7 Hz, 2H), 1.51 – 1.43 (m, 2H), 0.98 (t, J =
7.4 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 165.8, 139.2, 130.9, 128.9, 128.6, 65.1,
30.1, 19.2, 13.7.
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Butyl 3,4ꢀdichlorobenzoate (3ga CAS: 13050ꢀ59ꢀ4).14 The same procedure was used for
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2ꢀ(3,4ꢀdichlorophenyl)acetonitrile. The resulting solution was stirred at 130 C under O2
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(monitored by TLC and GC) for 9 hours. The reaction gave 94.7 mg of the product in 77%
yield as a light yellow oil. 1H NMR (500 MHz, CDCl3) δ 8.10 (d, J = 2.0 Hz, 1H), 7.86 (dd, J
= 8.4, 2.0 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 4.32 (t, J = 6.7 Hz, 2H), 1.76 (dd, J = 14.6, 7.2
Hz, 2H), 1.46 (dd, J = 15.0, 7.5 Hz, 2H), 0.98 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (125 MHz,
CDCl3) δ 164.8, 137.4, 132.8, 131.4, 130.5, 130.3, 128.6, 65.5, 30.7, 19.2, 13.7.
Butyl 3ꢀbromobenzoate (3ha CAS: 78987ꢀ67ꢀ4).17 The same procedure was used for
2ꢀ(3ꢀbromophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 104.1 mg of the product in 82%
as a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.16 (t, J = 1.8 Hz, 1H), 7.98 – 7.95
(m, 1H), 7.67 (m, 1H), 7.31 (t, J = 7.9 Hz, 1H), 4.33 (t, J = 6.6 Hz, 2H), 1.77 – 1.72 (m, 2H),
1.50 – 1.44 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 165.3,
135.7, 132.5, 132.4, 129.9, 128.1, 122.4, 65.3, 30.7, 19.2, 13.7.
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Butyl 4ꢀbromobenzoate (3ia CAS 120047ꢀ91ꢀ8).14 The same procedure was used for
2ꢀ(4ꢀbromophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 5 hours. The reaction gave 92.7 mg of the product in 72% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.00 – 7.82 (m, 2H), 7.66 – 7.49 (m, 2H),
4.32 (t, J = 6.6 Hz, 2H), 1.75 (dt, J = 14.5, 6.7 Hz, 2H), 1.52 – 1.42 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H).
13C{1H} NMR (126 MHz, CDCl3) δ 165.95, 131.66, 131.08, 129.42, 127.89, 65.13, 30.72, 19.26,
13.76.
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Butyl 2ꢀmethylbenzoate (3ja CAS: 65382ꢀ88ꢀ9).18 The same procedure was used for 2ꢀ(oꢀtolyl)
acetonitrile. The resulting solution was stirred at 130 oC under O2 (monitored by TLC and GC)
for 9 hours. The reaction gave 73.9 mg of the product in 77% as a light yellow oil liquid. 1H
NMR (500 MHz, CDCl3) δ 7.90 (dd, J = 8.1, 1.3 Hz, 1H), 7.39 (m, 1H), 7.26 – 7.12 (m, 2H),
4.30 (t, J = 6.6 Hz, 2H), 2.60 (s, 3H), 1.75 (m, 2H), 1.48 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H).
13C{1H} NMR (125 MHz, CDCl3) δ 167.8, 140.0, 131.8, 131.62, 130.5, 123.0, 125.6, 64.6,
30.8, 21.7, 19.3, 13.8.
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Butyl 3ꢀmethylbenzoate (3ka CAS: 6640ꢀ77ꢀ3).19 The same procedure was used for 2ꢀ(mꢀtolyl)
acetonitrile. The resulting solution was stirred at 130 oC under O2 (monitored by TLC and GC)
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for 9 hours. The reaction gave 78 mg of the product in 80% as a light yellow oil liquid. H
NMR (500 MHz, CDCl3) δ 7.85 (dd, J = 5.7, 5.0 Hz, 2H), 7.33 (m, 2H), 4.32 (t, J = 6.6 Hz,
2H), 2.40 (s, 3H), 1.78 – 1.71 (m, 2H), 1.51 – 1.45 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H). 13C{1H}
NMR (125 MHz, CDCl3) δ 166.9, 138.1, 133.5, 130.4, 130.0, 128.2, 126.6, 64.8, 30.8, 21.3,
19.3, 13.8.
Butyl 4ꢀmethylbenzoate (3la CAS: 19277ꢀ56ꢀ6).14 The same procedure was used for
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2ꢀ(pꢀtolyl)acetonitrile. The resulting solution was stirred at 130 C under O2 (monitored by
TLC and GC) for 5 hours. The reaction gave 81.6 mg of the product in 85% as a light
yellow oil solid. 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.0 Hz,
2H), 4.31 (t, J = 6.6 Hz, 2H), 2.40 (s, 3H), 1.75 (m, 2H), 1.48 (m, 2H), 0.98 (t, J = 7.4 Hz,
3H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.7, 143.4, 129.5, 128.98, 127.8, 64.6, 30.8, 21.6,
19.3, 13.8.
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Butyl 3ꢀmethoxybenzoate (3ma CAS: 77201ꢀ18ꢀ4).19 The same procedure was used for
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2ꢀ(3ꢀmethoxyphenyl) acetonitrile. The resulting solution was stirred at 130 C under O2
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(monitored by TLC and GC) for 9 hours. The reaction gave 79.1 mg of the product in 76% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 7.64 (d, J = 7.7 Hz, 1H), 7.58 – 7.53
(m, 1H), 7.34 (t, J = 7.9 Hz, 1H), 7.11 – 7.06 (m, 1H), 4.32 (t, J = 6.6 Hz, 2H), 3.85 (s, 3H),
1.74 (dd, J = 14.7, 7.0 Hz, 2H), 1.47 (dt, J = 14.7, 7.5 Hz, 2H), 0.98 (t, J = 7.4 Hz, 3H).
13C{1H} NMR (125 MHz, CDCl3) δ 166.5, 159.5, 131.8, 129.3, 121.9, 119.2, 114.1, 64.9,
55.4, 30.8, 19.3, 13.8.
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Butyl 3ꢀnitrobenzoate (3na CAS: 6268ꢀ25ꢀ3).20 The same procedure was used for
2ꢀ(3ꢀnitrophenyl) acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 80.1 mg of the product in 72% as
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a light yellow oil liquid. H NMR (500 MHz, CDCl3) δ 8.99 – 8.77 (m, 1H), 8.40 (m, 1H),
8.38 – 8.35 (m, 1H), 7.65 (t, J = 8.0 Hz, 1H), 4.38 (t, J = 6.7 Hz, 2H), 1.77 (dd, J = 14.8, 7.0
Hz, 2H), 1.52 – 1.45 (m, 2H), 0.99 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ
164.5, 148.2, 135.2, 132.2, 129.6, 127.2, 124.5, 65.8, 30.6, 19.2, 13.7.
Butyl 4ꢀnitrobenzoate (3oa CAS 120ꢀ48ꢀ9).21 The same procedure was used for
2ꢀ(4ꢀnitrophenyl) acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 83.6 mg of the product in 75% as
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a light yellow oil solid. H NMR (500 MHz, CDCl3) δ 8.35 – 8.24 (m, 2H), 8.23 – 8.17 (m,
2H), 4.37 (t, J = 6.6 Hz, 2H), 1.81 – 1.74 (m, 2H), 1.52 – 1.44 (m, 2H), 0.98 (t, J = 7.4 Hz,
3H). 13C{1H} NMR (125 MHz, CDCl3) δ 164.7, 150.4, 135.8, 130.6, 123.5, 65.8, 30.6, 19.2,
13.7.
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Butyl 4ꢀ(trifluoromethyl)benzoate (3pa CAS: 359803ꢀ67ꢀ1).22 The same procedure was used
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for 2ꢀ(4ꢀ(trifluoromethyl) phenyl) acetonitrile. The resulting solution was stirred at 130 C
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under O2 (monitored by TLC and GC) for 9 hours. The reaction gave 92.2 mg of the product
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in 75% as a light yellow oil liquid. H NMR (500 MHz, CDCl3) δ 8.15 (d, J = 8.1 Hz, 2H),
7.69 (d, J = 8.2 Hz, 2H), 4.36 (t, J = 6.6 Hz, 2H), 1.77 (m, 2H), 1.48 (m, 2H), 0.98 (t, J = 7.4
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Hz, 3H). C{1H} NMR (125 MHz, CDCl3) δ 165.4, 134.29 (q, J = 32.6 Hz), 133.71 (d, J =
1.0 Hz), 125.32 (q, J = 3.7 Hz), 123.64 (q, J = 272.7 Hz), 65.38, 30.66, 19.21 , 13.68 .
Butyl 4ꢀethynylbenzoate (3qa CAS: 137790ꢀ57ꢀ9).23 The same procedure was used for
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2ꢀ(4ꢀethynylphenyl) acetonitrile. The resulting solution was stirred at 130 C under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 76.8 mg of the product in 76% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.02 – 7.96 (m, 2H), 7.56 – 7.52 (m,
2H), 4.32 (t, J = 6.6 Hz, 2H), 3.22 (s, 1H), 1.76 (dd, J = 14.5, 7.2 Hz, 2H), 1.47 (dd, J = 15.0,
7.5 Hz, 2H), 0.98 (dd, J = 8.3, 6.5 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.0, 132.0,
130.5, 129.4, 126.6, 82.8, 79.9, 65.1, 30.7, 19.2, 13.7.
Butyl 4ꢀcyanobenzoate (3ra CAS: 29240ꢀ34ꢀ4).24 The same procedure was used for
4ꢀ(cyanomethyl)benzonitrile. The resulting solution was stirred at 130 oC under O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 79.2 mg of the product in 78% as a light
yellow oil solid. 1H NMR (500 MHz, CDCl3) δ 8.17 – 8.07 (m, 2H), 7.78 – 7.69 (m, 2H), 4.36
(t, J = 6.6 Hz, 2H), 1.79 – 1.71 (m, 2H), 1.48 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H). 13C{1H}
NMR (125 MHz, CDCl3) δ 165.0, 134.3, 132.2, 130.0, 118.0, 116.2, 65.6, 30.6, 19.2, 13.7.
Butyl 2ꢀnaphthoate (3sa CAS 3007ꢀ89ꢀ4).25 The same procedure was used for
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2ꢀ(naphthalenꢀ2ꢀyl) acetonitrile. The resulting solution was stirred at 130 C under O2
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(monitored by TLC and GC) for 5 hours. The reaction gave 80.9 mg of the product in 71% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.61 (s, 1H), 8.07 (dd, J = 8.6, 1.7 Hz,
1H), 7.96 (d, J = 8.1 Hz, 1H), 7.88 (d, J = 8.5 Hz, 2H), 7.61 – 7.49 (m, 2H), 4.40 (t, J = 6.7
Hz, 2H), 1.81 (m, 2H), 1.57 – 1.49 (m, 2H), 1.01 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (125
MHz, CDCl3) δ 166.8, 135.5, 132.5, 130.9, 129.3, 128.1, 128.1, 127.8, 127.7, 126.6, 125.2,
65.0, 30.8, 19.3, 13.8.
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Benzyl benzoate (3ab CAS 120ꢀ51ꢀ4).26 The same procedure was used for benzyl alcohol.
The resulting solution was stirred at 130 oC under O2 (monitored by TLC and GC) for 9 hours.
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The reaction gave 85.9 mg of the product in 81% as a light yellow oil liquid. H NMR (500
MHz, CDCl3) δ 8.21 – 8.07 (m, 2H), 7.62 – 7.56 (m, 1H), 7.51 – 7.36 (m, 7H), 5.41 (s, 2H).
13C{1H} NMR (125 MHz, CDCl3) δ 166.4, 136.0, 133.0, 130.1, 129.7, 128.6, 128.4, 128.2,
128.1, 66.7.
3ꢀmethylbenzyl benzoate (3ac CAS: 38612ꢀ03ꢀ2).27 The same procedure was used for
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3ꢀmethylbenzyl alcohol. The resulting solution was stirred at 130 C under O2 (monitored by
TLC and GC) for 9 hours. The reaction gave 92.4 mg of the product in 83% as a light yellow
oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.09 (d, J = 7.3 Hz, 2H), 7.60 – 7.52 (m, 1H), 7.44 (t,
J = 7.7 Hz, 2H), 7.31 – 7.26 (m, 2H), 7.16 (d, J = 7.1 Hz, 1H), 5.34 (s, 2H), 2.38 (s, 3H).
13C{1H} NMR (125 MHz, CDCl3) δ 166.4, 138.3, 135.9, 133.0, 130.2, 129.7, 129.0, 128.9,
128.5, 128.3, 125.2, 66.7, 21.4.
3ꢀbromobenzyl benzoate (3ad CAS：38612ꢀ14ꢀ5).28 The same procedure was used for
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3ꢀbromobenzyl alcohol. The resulting solution was stirred at 125 C under O2 (monitored by
TLC and GC) for 9 hours. The reaction gave 115 mg of the product in 80% as a light yellow
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oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.08 (dd, J = 8.2, 1.0 Hz, 2H), 7.61 – 7.55 (m, 2H),
7.46 (dd, J = 14.7, 6.9 Hz, 3H), 7.38 (d, J = 7.7 Hz, 1H), 7.28 – 7.25 (m, 1H), 5.33 (s, 2H).
13C{1H} NMR (125 MHz, CDCl3) δ 166.2, 138.3, 133.2, 131.3, 131.0, 130.2, 129.8, 129.7,
128.4, 126.6, 122.6, 65.7.
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2ꢀchlorobenzyl benzoate (3ae CAS：882042ꢀ79ꢀ7).29 The same procedure was used for
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2ꢀchlorobenzylalcohol. The resulting solution was stirred at 130 C under O2 (monitored by
TLC and GC) for 9 hours. The reaction gave 88.6 mg of the product in 72% as a light yellow
oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.19 – 8.05 (m, 2H), 7.63 – 7.56 (m, 1H), 7.52 (dd, J
= 5.7, 3.6 Hz, 1H), 7.47 – 7.41 (m, 3H), 7.31 – 7.28 (m, 2H), 5.48 (s, 2H). 13C{1H} NMR
(125 MHz, CDCl3) δ 166.2, 133.7, 133.1, 129.9, 129.8, 129.7, 129.6, 129.5, 128.4, 126.9,
64.0.
3ꢀchlorophenethyl benzoate (3af). The same procedure was used for 3ꢀchlorophenethyl
alcohol. The resulting solution was stirred at 130 oC under O2 (monitored by TLC and GC) for
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9 hours. The reaction gave 96.2 mg of the product in 74% as a light yellow oil liquid. H
NMR (500 MHz, CDCl3) δ 8.12 – 7.91 (m, 2H), 7.59 – 7.51 (m, 1H), 7.44 (dd, J = 10.7, 4.8
Hz, 2H), 7.30 (s, 1H), 7.28 – 7.22 (m, 2H), 7.17 (dd, J = 6.8, 1.7 Hz, 1H), 4.53 (t, J = 6.9 Hz,
2H), 3.06 (t, J = 6.9 Hz, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.4, 139.9, 134.2, 133.0,
130.1, 129.8, 129.5, 129.1, 128.4, 127.1, 126.8, 64.9, 34.9. HRMS(MALDI DHB) m/z
[M+H]+ calcd for C15H14O2Cl, 261.0677, found 261.0674.
Phenethyl benzoate (3ag CAS: 94ꢀ47ꢀ3).27 The same procedure was used for phenethyl
alcohol. The resulting solution was stirred at 130 oC under O2 (monitored by TLC and GC) for
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9 hours. The reaction gave 80.2 mg of the product in 71% as a light yellow oil liquid. H
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NMR (500 MHz, CDCl3) δ 8.05 (dd, J = 8.1, 0.9 Hz, 2H), 7.62 – 7.53 (m, 1H), 7.47 – 7.41 (m,
2H), 7.34 (m, 4H), 7.29 – 7.25 (m, 1H), 4.56 (t, J = 7.0 Hz, 2H), 3.11 (t, J = 7.0 Hz, 2H).
13C{1H} NMR (125 MHz, CDCl3) δ 166.5, 137.9, 132.8, 130.2, 129.5, 128.9, 128.5, 128.3,
126.5, 65.4, 35.2.
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4ꢀmethoxyphenethyl benzoate (3ah CAS 174681ꢀ77ꢀ7).27 The same procedure was used for
3ꢀmethoxyphenethyl alcohol. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 92.1 mg of the product in 72% as
a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.03 (dd, J = 8.3, 1.3 Hz, 2H), 7.56 (m,
1H), 7.47 – 7.39 (m, 2H), 7.23 – 7.16 (m, 2H), 6.90 – 6.83 (m, 2H), 4.51 (t, J = 7.0 Hz, 2H),
3.80 (s, 3H), 3.03 (t, J = 7.0 Hz, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.5., 158.3,
132.8, 130.3, 129.9, 129.5, 128.3, 113.9, 65.7, 55.2, 34.3.
2ꢀ(thiophenꢀ3ꢀyl)ethyl benzoate (3ai CAS: 198278ꢀ19ꢀ2). The same procedure was used for
thiopheneꢀ3ꢀethanol. The resulting solution was stirred at 130 oCunder O2 (monitored by TLC
and GC) for 9 hours. The reaction gave 84.7 mg of the product in 73% as a light yellow oil
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liquid. H NMR (500 MHz, CDCl3) δ 8.08 – 7.82 (m, 2H), 7.61 – 7.52 (m, 1H), 7.50 – 7.41
(m, 2H), 7.29 (dd, J = 4.9, 3.0 Hz, 1H), 7.17 – 7.07 (m, 1H), 7.04 (dd, J = 4.9, 1.2 Hz, 1H),
4.54 (t, J = 6.9 Hz, 2H), 3.13 (t, J = 6.9 Hz, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.5,
138.1, 132.9, 130.2, 129.5, 128.3, 128.3, 125.7, 121.6, 64.8, 29.7. HRMS (DART Positive)
m/z [M+H]+ calcd for C13H13O2S, 233.0631, found 233.0628.
2ꢀ(thiophenꢀ2ꢀyl)ethyl benzoate (3aj CAS: 1044504ꢀ84ꢀ8).30 The same procedure was used
o
for thiopheneꢀ2ꢀethanol. The resulting solution was stirred at 130 C under O2 (monitored by
TLC and GC) for 9 hours. The reaction gave 81.2 mg of the product in 70% as a light yellow
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oil liquid 1H NMR (500 MHz, CDCl3) δ 8.08 (dd, J = 8.1, 0.9 Hz, 2H), 7.62 – 7.52 (m, 1H),
7.45 (dd, J = 10.8, 4.7 Hz, 2H), 7.18 (dd, J = 5.1, 1.2 Hz, 1H), 7.02 – 6.87 (m, 2H), 4.56 (t, J
= 6.6 Hz, 2H), 3.31 (t, J = 6.6 Hz, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.4, 140.0,
133.0, 130.1, 129.6, 128.4, 126.9, 125.6, 124.1, 65.2, 29.4.
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Ethyl benzoate (3ak CAS 93ꢀ89ꢀ0).31 The same procedure was used for ethanol. The resulting
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solution was stirred at 130 C under O2 (monitored by TLC and GC) for 15 hours. The
reaction gave 53.2 mg of the product in 71% as a colorless oil. 1H NMR (500 MHz, CDCl3) δ
8.10 – 7.95 (m, 2H), 7.57 – 7.51 (m, 1H), 7.46 – 7.36 (m, 2H), 4.38 (q, J = 7.1 Hz, 2H), 1.40
(t, J = 7.1 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 166.6, 132.8, 130.5, 129.5, 128.3,
60.9, 14.3.
Phenyl benzoate (3al CAS 93ꢀ99ꢀ2).32 The same procedure was used for phenol. The resulting
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solution was stirred at 130 C under O2 (monitored by TLC and GC) for 15 hours. The
reaction gave 62.4mg of the product in 62% as a white liquid. 1H NMR (500 MHz, CDCl3) δ
8.22 (dd, J = 8.2, 1.1 Hz, 2H), 7.67 – 7.62 (m, 1H), 7.54 – 7.49 (m, 2H), 7.46 – 7.42 (m, 2H),
7.28 (dd, J = 10.7, 4.2 Hz, 1H), 7.24 – 7.19 (m, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ
165.2, 151.0, 133.6, 130.2, 129.6, 129.5, 128.6, 125.9, 121.7.
4ꢀbromophenyl benzoate (3am CAS 1523ꢀ17ꢀ7).33 The same procedure was used for
4ꢀbromophenol. The resulting solution was stirred at 130 oC under O2 (monitored by TLC and
GC) for 15 hours. The reaction gave 90.7 mg of the product in 66% as a light yellow oil liquid.
1H NMR (500 MHz, CDCl3) δ 8.23 – 8.14 (m, 2H), 7.68 – 7.62 (m, 1H), 7.57 – 7.50 (m, 4H),
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7.16 – 7.07 (m, 2H). C{1H} NMR (125 MHz, CDCl3) δ 164.8, 150.0, 133.8, 132.5, 130.2,
129.2, 128.6, 123.5, 119.0.
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4ꢀchlorophenyl benzoate (3an CAS 2005ꢀ08ꢀ5).34 The same procedure was used for
4ꢀchlorophenol. The resulting solution was stirred at 130 oC under O2 (monitored by TLC and
GC) for 15 hours. The reaction gave 78.9 mg of the product in 68% as a light yellow oil. 1H
NMR (500 MHz, CDCl3) δ 8.24 – 8.13 (m, 2H), 7.68 – 7.63 (m, 1H), 7.55 – 7.47 (m, 2H),
7.44 – 7.35 (m, 2H), 7.21 – 7.12 (m, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 164.9, 149.4,
133.8, 131.3, 130.2, 129.5, 129.2, 128.6, 123.1.
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Perfluorophenyl benzoate (3ao CAS 1548ꢀ84ꢀ1).35 The same procedure was used for
2,3,4,5,6ꢀPentafluorophenol. The resulting solution was stirred at 130 oC under O2 (monitored
by TLC and GC) for 24 hours. The reaction gave 74.8 mg of the product in 51% as a light
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yellow oil liquid. H NMR (500 MHz, CDCl3) δ 8.20 (m, 2H), 7.73 – 7.67 (m, 1H), 7.60 –
7.52 (m, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 162.6, 143.0 – 142.0 (m), 140.7 – 134.0
(m), 139.2 – 138.7 (m), 137.3 – 136.6 (m), 134.7, 130.7 , 128.9, 127.0.
(1R,2S,4S)ꢀ2ꢀisopropylꢀ4ꢀmethylcyclohexyl benzoate (3ap). The same procedure was used for
o
(±)ꢀmenthol. The resulting solution was stirred at 130 C under O2 (monitored by TLC and
GC) for 24 hours. The reaction gave 92.3 mg of the product in 71% as a light yellow oil liquid.
1H NMR (500 MHz, CDCl3) δ 8.21 – 7.94 (m, 2H), 7.58 – 7.50 (m, 1H), 7.47 – 7.37 (m, 2H),
4.94 (m, 1H), 2.17 – 2.09 (m, 1H), 1.97 (m, 1H), 1.77 – 1.70 (m, 2H), 1.56 (m, 2H), 1.19 –
1.07 (m, 2H), 0.93 (dd, J = 6.8, 4.9 Hz, 7H), 0.80 (d, J = 7.0 Hz, 3H). 13C{1H} NMR (125
MHz, CDCl3) δ 166.1, 132.6, 130.8, 129.5, 128.3, 74.8, 47.3, 41, 34.3, 31.4, 26.5, 23.6, 22.0,
20.7, 16.5. HRMS(EI) m/z [M+H]+ calcd for C17H25O2, 261.1849, found 261.1847.
2ꢀ((1S,5R)ꢀ6,6ꢀdimethylbicyclo[3.1.1]heptꢀ2ꢀenꢀ3ꢀyl)ethyl benzoate (3aq). The same
o
procedure was used for 3ꢀpentanol. The resulting solution was stirred at 135 C under O2
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(monitored by TLC and GC) for 28 hours. The reaction gave 73.3 mg of the product in 67%
as a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.17 – 7.91 (m, 2H), 7.59 – 7.51
(m, 1H), 7.49 – 7.38 (m, 2H), 5.41 – 5.34 (m, 1H), 4.40 – 4.27 (m, 2H), 2.46 – 2.40 (m, 2H),
2.39 – 2.35 (m, 1H), 2.33 – 2.16 (m, 3H), 2.13 (td, J = 5.7, 1.2 Hz, 1H), 2.11 – 2.07 (m, 1H),
1.27 (s, 3H), 0.84 (s, 3H).13C{1H} NMR (125 MHz, CDCl3) δ 166.5, 144.2, 132.8, 130.4,
129.5, 128.3, 118.9, 63.3, 45.8, 40.7, 38.0, 36.1, 31.7, 31.4, 26.3, 21.1. HRMS(EI) m/z
[M+H]+ calcd for C18H23O2, 271.1693, found 271.1691.
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(1S,2R,4R)ꢀ1,7,7,7ꢀtetramethylꢀ7λ5ꢀbicyclo[2.2.1]heptanꢀ2ꢀyl
benzoate
(3ar
CAS:
122922ꢀ36ꢀ5).36 The same procedure was used for (ꢀ)ꢀborneol. The resulting solution was
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stirred at 130 Cunder O2 (monitored by TLC and GC) for 24 hours. The reaction gave 84.6
mg of the product in 63% as a light yellow oil liquid. 1H NMR (500 MHz, CDCl3) δ 8.07 (dd,
J = 7.9, 0.9 Hz, 2H), 7.55 (m, 1H), 7.48 – 7.41 (m, 2H), 5.22 – 5.08 (m, 1H), 2.52 – 2.45 (m,
1H), 2.18 – 2.12 (m, 1H), 1.85 – 1.77 (m, 1H), 1.74 (t, J = 4.5 Hz, 1H), 1.42 (m, 1H), 1.34 –
1.29 (m, 1H), 1.13 (dd, J = 13.8, 3.5 Hz, 1H), 0.97 (s, 3H), 0.92 (s, 6H). 13C{1H} NMR (125
MHz, CDCl3) δ 166.8, 132.7, 130.9, 129.5, 128.3, 80.5, 49.1, 47.9, 45.0, 36.9, 28.1, 27.4,
19.7, 18.9, 13.6.
(3S,8S,9S,10R,13R,14S,17R)ꢀ10,13ꢀdimethylꢀ17ꢀ((R)ꢀ6ꢀmethylheptanꢀ2ꢀyl)ꢀ2,3,4,7,8,9,10,11,1
2,13,14,15,16,17ꢀtetradecahydroꢀ1Hꢀcyclopenta[a]phenanthrenꢀ3ꢀyl
benzoate
(3as
CAS:604ꢀ32ꢀ0).31 The same procedure was used for cholesterol. The resulting solution was
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stirred at 130 C under O2 (monitored by TLC and GC) for 35 hours. The reaction gave 109
mg of the product in 43% yield as a white solid. 1H NMR (500 MHz, CDCl3) δ 8.07 – 8.01 (m,
2H), 7.58 – 7.51 (m, 1H), 7.43 (dd, J = 10.7, 4.7 Hz, 2H), 5.42 (d, J = 3.8 Hz, 1H), 4.92 –
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4.80 (m, 1H), 2.47 (d, J = 7.7 Hz, 2H), 2.05 – 1.98 (m, 3H), 1.92 (dt, J = 13.3, 3.4 Hz, 1H),
1.84 (m, 1H), 1.78 – 1.70 (m, 1H), 1.58 – 1.44 (m, 6H), 1.39 – 1.33 (m, 3H), 1.29 – 1.24 (m,
2H), 1.20 (dd, J = 16.0, 4.0 Hz, 2H), 1.15 – 1.09 (m, 4H), 1.07 (s, 3H), 1.04 – 0.99 (m, 3H),
0.93 (d, J = 6.5 Hz, 3H), 0.87 (dd, J = 6.6, 2.2 Hz, 6H), 0.69 (s, 3H). 13C{1H} NMR (125
MHz, CDCl3) δ 166.0, 139.6, 132.7, 130.8, 129.5, 128.2, 122.8, 74.6, 56.7, 56.1, 50.0, 42.3,
39.7, 39.5, 38.2, 37.0, 36.6, 36.2, 35.8, 31.9, 31.9, 28.2, 28.0, 27.9, 24.3, 23.8, 22.8, 22.6, 21.0,
19.4, 18.7, 11.9.
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methyl benzoate (3at CAS:93ꢀ58ꢀ3).37 The same procedure was used fortrimethyl borate. The
resulting solution was stirred at 130 oCunder O2 (monitored by TLC and GC) for 9 hours. The
reaction gave 62mg of the product in 91% as a colorless liquid. 1H NMR (500 MHz, CDCl3) δ
8.04 (dd, J = 8.4, 1.3 Hz, 2H), 7.58 – 7.53 (m, 1H), 7.48 – 7.41 (m, 2H), 3.92 (s, 3H).13C{1H}
NMR (126 MHz, CDCl3) δ 167.1, 132.9, 130.1, 129.6, 128.3, 52.1.
methyl benzoate (3’at CAS:93ꢀ58ꢀ3 ).37 The same procedure was used for trimethyl borate.
The resulting solution was stirred at 130 oC under O2 (monitored by TLC and GC) for 9 hours.
The reaction gave 56mg of the product in 89% as a liquid.1H NMR (500 MHz, CDCl3) δ 8.07
– 7.97 (m, 2H), 7.59 – 7.50 (m, 1H), 7.43 (dd, J = 10.8, 4.8 Hz, 2H), 3.91 (s, 3H).13C{1H}
NMR (126 MHz, CDCl3) δ 167.0, 132.8, 130.1, 129.5, 128.3, 52.0.
propyl benzoate (3au CAS：2315ꢀ68ꢀ6).38 The same procedure was used tripropyl borate. The
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resulting solution was stirred at 130 C under O2 (monitored by TLC and GC) for 9 hours.
The reaction gave 73 mg of the product in 90% as a colorless liquid. 1H NMR (500 MHz,
CDCl3) δ 8.28 – 7.89 (m, 1H), 7.61 – 7.51 (m, 1H), 7.49 – 7.39 (m, 1H), 4.29 (t, J = 6.7 Hz,
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1H), 1.90 – 1.72 (m, 1H), 1.04 (t, J = 7.4 Hz, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ
166.70, 132.79, 130.53, 129.53, 128.32, 66.54, 22.13, 10.54.
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methyl 4ꢀmethylbenzoate (3lt CAS ： 99ꢀ75ꢀ2).38 The same procedure was used
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2ꢀ(pꢀtolyl)acetonitrile. The resulting solution was stirred at 130 C under O2 (monitored by
TLC and GC) for 9 hours. The reaction gave 67mg of the product in 89% as a white solid.1H
NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 3.90 (s, 3H),
2.41 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 167.2, 143.5, 129.6, 129.1, 127.5, 51.9,
21.6.
methyl 4ꢀmethylbenzoate (3’lt CAS ： 99ꢀ75ꢀ2).38 The same procedure was used
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2ꢀ(pꢀtolyl)acetonitrile. The resulting solution was stirred at 130 C under O2 (monitored by
TLC and GC) for 9 hours. The reaction gave 62mg of the product in 82% as a white solid, 1H
NMR (500 MHz, CDCl3) δ 7.96 – 7.90 (m, 2H), 7.23 (d, J = 8.0 Hz, 2H), 3.90 (s, 3H), 2.41 (s,
3H).13C{1H} NMR (126 MHz, CDCl3) δ 167.2, 143.5, 129.6, 129.0, 127.4, 51.9, 21.6.
methyl 4ꢀchlorobenzoate (3ft CAS: 1126ꢀ46ꢀ1).39 The same procedure was used
2ꢀ(4ꢀchlorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 62 mg of the product in 76% as a
white solid.1H NMR (500 MHz, CDCl3) δ 8.00 – 7.94 (m, 2H), 7.44 – 7.37 (m, 2H), 3.91 (s,
3H).13C{1H} NMR (126 MHz, CDCl3) δ 166.2, 139.3, 130.9, 128.7, 128.6, 52.2.
methyl 4ꢀchlorobenzoate (3’ft CAS: 1126ꢀ46ꢀ1).39 The same procedure was used
2ꢀ(4ꢀchlorophenyl)acetonitrile. The resulting solution was stirred at 130 oC under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 62 mg of the product in 76% as a
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white solid,.1H NMR (500 MHz, CDCl3) δ 8.02 – 7.91 (m, 2H), 7.45 – 7.36 (m, 2H), 3.91 (s,
3H).13C{1H} NMR (126 MHz, CDCl3) δ 166.2, 139.3, 130.9, 128.7, 128.5, 52.2.
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methyl 4ꢀnitrobenzoate (3ot CAS: 619ꢀ50ꢀ1).39 The same procedure was used
2ꢀ(4ꢀnitrophenyl)acetonitrile. The resulting solution was stirred at 130 oCunder O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 82 mg of the product in 90% as a white
solid.1H NMR (500 MHz, CDCl3) δ 8.33 – 8.15 (m, 4H), 3.97 (s, 3H).13C{1H} NMR (126
MHz, CDCl3) δ 165.1, 150.5, 135.5, 130.7, 123.5, 52.8.
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methyl 4ꢀnitrobenzoate (3’ot CAS: 619ꢀ50ꢀ1).39 The same procedure was used
2ꢀ(4ꢀnitrophenyl)acetonitrile. The resulting solution was stirred at 130 oCunder O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 71mg of the product in 78% as a white
solid.1H NMR (500 MHz, CDCl3) δ 8.35 – 8.24 (m, 2H), 8.20 (d, J = 7.6 Hz, 2H), 3.97 (s,
3H).13C{1H} NMR (126 MHz, CDCl3) δ 165.1, 150.5, 135.5, 130.7, 123.5, 52.8.
methyl 4ꢀnitrobenzoate (3”ot CAS: 619ꢀ50ꢀ1).39 The same procedure was used
2ꢀ(4ꢀnitrophenyl)acetonitrile. The resulting solution was stirred at 130 oCunder O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 76mg of the product in 84% as a white
solid.1H NMR (500 MHz, CDCl3) δ 8.31 – 8.25 (m, 2H), 8.22 – 8.17 (m, 2H), 3.97 (s,
3H).13C{1H} NMR (126 MHz, CDCl3) δ 165.1, 150.5, 135.5, 130.7, 123.5, 52.8.
methyl 3ꢀnitrobenzoate (3nt CAS:618ꢀ95ꢀ1).40 The same procedure was used
2ꢀ(3ꢀnitrophenyl)acetonitrile. The resulting solution was stirred at 130 oCunder O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 67mg of the product in 74% yield as a white
solid.1H NMR (500 MHz, CDCl3) δ 8.83 (s, 1H), 8.43 – 8.33 (m, 2H), 7.64 (t, J = 8.0 Hz,
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1H), 3.97 (d, J = 0.9 Hz, 3H).13C{1H} NMR (126 MHz, CDCl3) δ 165.1, 150.5, 135.5, 130.7,
123.5, 52.8.
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methyl 3ꢀnitrobenzoate (3’nt CAS:618ꢀ95ꢀ1).40 The same procedure was used
2ꢀ(3ꢀnitrophenyl)acetonitrile. The resulting solution was stirred at 130 oCunder O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 66 mg of the product in 72% yield as a white
solid.1H NMR (500 MHz, CDCl3) δ 8.83 (s, 1H), 8.43 – 8.33 (m, 2H), 7.64 (t, J = 8.0 Hz,
1H), 3.97 (d, J = 0.9 Hz, 3H).13C{1H} NMR (126 MHz, CDCl3) δ 165.1, 150.5, 135.5, 130.7,
123.5, 52.8.
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methyl 3ꢀnitrobenzoate (3”nt CAS:618ꢀ95ꢀ1).9c The same procedure was used
2ꢀ(3ꢀnitrophenyl)acetonitrile. The resulting solution was stirred at 130 oCunder O2 (monitored
by TLC and GC) for 9 hours. The reaction gave 73 mg of the product in 80% yield as a white
solid.1H NMR (500 MHz, CDCl3) δ 8.83 (s, 1H), 8.43 – 8.33 (m, 2H), 7.64 (t, J = 8.0 Hz,
1H), 3.97 (d, J = 0.9 Hz, 3H).13C{1H} NMR (126 MHz, CDCl3) δ 165.1, 150.5, 135.5, 130.7,
123.5, 52.8.
methyl 4ꢀmethoxybenzoate (3’tt CAS:121ꢀ98ꢀ2).39 The same procedure was used
o
2ꢀ(4ꢀmethoxyphenyl)acetonitrile. The resulting solution was stirred at 130 C under O2
(monitored by TLC and GC) for 9 hours. The reaction gave 73 mg of the product in 88%
yield as white solid, 1H NMR (500 MHz, CDCl3) δ 7.98 (d, J = 9.0 Hz, 2H), 6.91 (d, J = 8.9
Hz, 2H), 3.87 (s, 3H), 3.85 (s, 3H).13C{1H} NMR (126 MHz, CDCl3) δ 166.8, 163.3, 131.5,
122.6, 113.5, 55.4, 51.8.
AUTHOR INFORMATION
Corresponding Author
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*Eꢀmail: qsong@hqu.edu.cn.
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Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENT
Financial support from the National NaturalScience Foundation of China (21202049),
the Recruitment Program of Global Experts (1000 Talents Plan), the Natural Science
Foundation of Fujian Province (2016J01064), Fujian Hundred Talents Plan and Program of
Innovative Research Team of Huaqiao University (Z14X0047) are gratefully acknowledged.
We also thank Instrumental Analysis Center of Huaqiao University for analysis support.
ASSOCIATED CONTENT
Supporting Information
Supplementary condition screens, preliminary mechanistic studies and NMR spectra of
all products. This material is available free of charge via the Internet at http://pubs.acs.org.
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