SO2F2-Mediated One-Pot Synthesis of Aryl Carboxylic Acids and Esters from Phenols through a Pd-Catalyzed Insertion of Carbon Monoxide

Article abstract of DOI:10.1002/asia.201700891

A one-pot Pd-catalyzed carbonylation of phenols into their corresponding aryl carboxylic acids and esters through the insertion of carbon monoxide has been developed. This procedure offers a direct synthesis of aryl carboxylic acids and esters from inexpensive and abundant starting materials (phenols, SO₂F₂ and CO) under mild conditions. This method tolerates a broad range of functional groups and is also applicable for the modification of complicated natural products.

Full text of DOI:10.1002/asia.201700891

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: SO2F2 Mediated One-Pot Synthesis of Arylcarboxylic Acids
and Esters from Phenols via a Pd-Catalyzed Carbon Monoxide
Insertion
Authors: Wan-Yin Fang, Jing Leng, and Hua-Li Qin
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10.1002/asia.201700891
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SO2F2 Mediated One-Pot Synthesis of Arylcarboxylic Acids and
Esters from Phenols via a Pd-Catalyzed Carbon Monoxide
Insertion
Wan-Yin Fang, [a] Jing Leng, [a] Hua-Li Qin *[a]
Abstract: A one-pot Pd-catalyzed carbonylation of phenols to their
corresponding arylcarboxylic acids and esters through the insertion
of carbon monoxide is developed. This protocol provides a mild
condition for direct synthesis of arylcarboxylic acids and esters from
inexpensive and abundant starting materials of phenols, SO2F2 and
CO. This method was found to tolerate a broad of functional groups
and was also applicable for modification of complicated natural
products.
production of phenols is up to millions of tons.[7] Phenols and
their salts derivatives have been successfully employed as
substitutes of aryl halides in Pd and Ni catalyzed transformations.
[8]
In addition, the phenols derived aryl tosylates and mesylates
have also been successfully applied for Pd-catalyzed
carbonylative synthesis of aryl carboxylic acids employing CO as
C1 source.[9] Aryl fluorosulfonates, prepared in high yields and
under mild condition from the reaction of the corresponding
phenols and sulfuryl fluoride (SO2F2), offering an inexpensive
alternative to aryl halides and other aryl sulfonates.[10]
Meanwhile, aryl fluorosulfonates were also described to have a
similar functionality to aryl triflates or aryl halides to participate in
various transformations.[11] Accordingly, the development of
novel methods, taking advantages of the abundant and
inexpensive supply of sulfuryl fluoride (SO2F2), carbon monoxide
(CO) and phenols (ArOH) for the transformation of phenols to
their corresponding arylcarboxylic acids and esters, provides a
significant attractive option for the assemble of carboxylic acid
Introduction
Carboxylic acids and esters are important classes of chemicals
presented in pharmaceuticals, polymers, agrochemicals, natural
products and biological systems and also have wide application
as versatile building blocks in organic synthesis.[1] Therefore, the
development of efficient and practical methods for the synthesis
of carboxylic acids is of great importance. Up to date, various
methods have been developed for the construction of carboxylic
acids and esters. The utilization of CO2 as a C1-synthon source
to be incorporated with lithium phenolate or Grignard reagents
for the synthesis of carboxylic acids has been well known for
more than a century.[2] Transition metal catalyzed direct insertion
of CO2 into aryl halides is another valuable method for the
preparation of aryl carboxylic acids with high selectivity and
under mild conditions.[3] Besides the utilization of CO2 as a C1-
synthon for the synthesis of carboxylic acids and esters, the Pd-
catalyzed carbonylation of aryl halides taking advantage of CO
as an inexpensive and readily available C1 source is another
interesting and complementary transformation.[4] Pioneered by
Heck and co-workers,[5] these carbonylation reactions have been
extensively utilized in organic synthesis and industrial
processes.[6] Compared to aryl halides, phenols are particularly
more attractive starting materials because most of them are
readily available from fuel and biomass and the world annual
derivatives. Herein, we report
a
one-pot Pd-catalyzed
carbonylation of phenols to their corresponding aryl carboxylic
acids and esters through the insertion of carbon monoxide via
the aryl fluorosulfonate intermediates. Unlike typical Pd-
catalyzed carbon monoxide insertion type of carbonylation of
aryl halides, which generally requires elevated temperatures
12]
(≥80 oC) and/ or relatively high pressure (>5 bar),[6b,
this
scalable one-pot practical protocol distinguishes itself with milder
operation condition and high efficiency properties.[13]
Results and Discussion
We conducted our initial study with 4-hydroxybiphenyl 1a as
model substrate to examine the feasibility of this transformation
(Table 1). Accordingly, fluorosulfonate 2a was accomplished by
the reaction of 4-hydroxybiphenyl 1a with sulfuryl fluoride (SO2F2)
in nearly quantitative yield.[6a] Without further purification,
fluorosulfonate 2a was subjected to carbonylation with CO and
water for the formation of carboxylic acid 3a.
[a]
Wan-Yin Fang, Jing Leng, Hua-Li Qin
After screening of a variety of conditions, as shown in Table 1,
we are delighted to find a mild procedure to convert 4-
hydroxybiphenyl 1a to the corresponding carboxylic acid 3a via
the key fluorosulfonate 2a intermediate in excellent yield (Table
1, entry 15). The use of additional organic or inorganic base
(Et3N or NaHCO3) is essential for the Pd-catalyzed carbon
monoxide insertion process, particularly, the reaction proceeded
much more efficiently when NaHCO3 was added to the reaction
State Key Laboratory of Silicate Materials for Architectures; and
School of Chemistry, Chemical Engineering and Life Science
Wuhan University of Technology
205 Luoshi Road, Wuhan, Hubei Province, 430070 (P. R. China)
E-mail: qinhuali@whut.edu.cn
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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Table 1 Optimization of the Reaction Conditions
Pd cat.
Ligand
Yield
Entry
Additive (eq)
T (oC)
(mol %)
(mol %)
(3a,a,b
)
1
2
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(MeCN)2Cl2 (5)
Pd(PPh3)4 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (3)
Pd(OAc)2 (1)
Pd(OAc)2 (3)
Pd(OAc)2 (3)
Pd(OAc)2 (3)
Pd(OAc)2 (3)
Pd(OAc)2 (3)
PPh3 (5)
P(o-tolyl)3 (5)
PCy3 (5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0), NaHCO3 (1.5)
Et3N (2.0)
70
70
70
70
70
70
70
70
70
70
70
70
70
60
40
r.t.
70
70
< 1
< 1
< 1
85
6
3
4
BINAP (5)
DPPE (5)
DPPF (5)
DPPP (5)
DPPP(5)
DPPP (5)
DPPP (5)
DPPP (5)
DPPP (3)
DPPP (1)
DPPP (3)
DPPP (3)
DPPP (3)
DPPP (0)
DPPP (3)
5
6
59
97
42
87
72
96
95
86
95
86
53
<1
<3
7
8
9
10
11
13
14
15
16
17
18
19
NaHCO3 (1.5)
NaHCO3 (1.5)
NaHCO3 (1.5)
NaHCO3 (1.5)
NaHCO3 (1.5)
NaHCO3 (1.5)
NaHCO3 (1.5)
Et3N (0), NaHCO3 (0)
[a] General procedure for the carbonylation: a mixture of 4-phenylphenol (1a, 0.3 mmol), Et3N (0.6mmol, 2 eq), DMSO (1.0 mL) was stirred at r.t. charged with a
SO2F2 balloon for 2 hours before Palladium catalyst, Ligand, NaHCO3 or/ and Et3N and H2O (40 eq) were added into the mixture to react for an additional 12 h
under CO atmosphere (a CO balloon) at the corresponding temperature. [b] Yields were determined by HPLC using the pure 4-biphenylcarboxylic acid (3a, 0.3
mmol) as the internal standard (tR = 4.071 min, λmax = 265.4 nm, CH3CN/CH3CO2NH4 (5 mmol/L) = 30 : 70 (v / v).
solution (Table 1, entry 1-19). It is worth to note, the use of
monodentate ligands, such as PPh3, PCy3 and (o-tolyl)3,
provided only a trace amount of the desired product (Table 1,
entries 1–3), while the bidentate phosphine ligands, such as
DPPP, DPPE, DPPF and BINAP promoted the carbonylation
significantly (Table 1, entries 4–17). It is noteworthy that ligand
DPPP, 1, 3-bis(diphenylphosphino)-propane, accelerated this
transformation more efficiently than its bidentate phosphine
counterparties (DPPE, DPPF and BINAP) (Table 1, entries 4–7).
Further optimization showed that the Pd-catalyzed carbon
monoxide insertion process could be operated at room
temperature and without high pressure but still provided the
desired carboxylic acid in moderate yield (53 %, Table 1, entries
(Table 1, entries 7-9). The screening of catalyst loading showed
that 3 % loading of Pd(OAc)2 catalyst is more suitable for this
transformation even though 1 % loading was still able to provide
the carbonylation in excellent yield (Table 1, entries 13-14).
With the optimized catalytic system in hand, we subsequently
set to explore the substrate scope and functional group
tolerance of the Palladium-catalyzed carbonylation process with
a variety of phenols (Table 2). Subsequently, twenty different
phenols were successfully transformed to their corresponding
acids with this developed method as illustrated in Table 2. In
most cases, the corresponding aromatic carboxylic acids were
obtained in good to excellent yields among a range of electron-
donating and electron-withdrawing substituent on the ortho-,
meta-, and para- positions of the aromatic rings. Aromatic
groups (3a, 3s and 3t), alkyl groups (3c-e and 3r), ether (3f-h),
trifluomethyl (3i-k), halogen (3l, 3p and 3q), cyano (3m), ester
(3n), formyl (3o) were all well-tolerated under the developed
reaction condition. It is interesting to find that phenols containing
electron-withdrawing functionalities generally provided their
o
17), raising the temperature to 40 C increased the yield of the
reaction to 86 % (Table 1, entries 16). However, further
increasing the reaction temperature above 60 oC did not
promote the yield of carboxylic acid (Table 1, entries 13, 15).
It is noteworthy that Pd(OAc)2 catalyzed this carbonylation
more efficiently than Pd(MeCN)2Cl2 and Pd(PPh3)4 partners
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corresponding acids in a better yield while phenols containing
electron-donating groups afforded their products in a relatively
lower yield. For example, the carbonylation of 1i, 1j, 1o and 1p
with electron-withdrawing substituents on the aromatic ring
occurred in excellent yields (about 90 %), while the substrates
with a strong electron-donating methoxyl group (1f-h) or two
methyl groups (1r) only provided their corresponding acids in
less than 65 % yield. Notably, the position of substituents on the
phenyl rings of phenols has some influence on the reaction.
Sterically encumbered substrates often gave lower yields, such
as methyl substituted phenol 1e comparing to 1c and 1d; and
bromo substituted phenol 1q comparing to 1l. Gratefully, some
non-substituted phenols or para-electron-rich groups substituted
substrates 1a, 1b, 1s and 1t, were also converted to the
expected products in nearly quantitative yield.
However, to our delight, these sterically encumbered phenols
(1e, 1o) still furnished their corresponding esters (4e, 4o) in
good yields when the loading of Pd(OAc)2 and DPPP were
increased to 5 mol %. It is also found that the steric hindrance of
alcohols also affected the esterification yields significantly, the
utilizing of methanol or ethanol as nucleophiles afforded the
esters in much higher yields than the isopropanol as nucleophile
(4ma, 4mb, 4mc). It is noteworthy, the catalytic system
distinguished between fluorosulfonate and other potential
reactive halides (F, Cl, Br) for esterification (4p, 4q, 4u).
Bisphenol resorcine (1w) was also converted to bisester 4w in
good yield when the stoichiometry of reagents was adjusted
accordingly. Both the homo-esterification of phenols and the
hetero-esterification of two different phenols were also
successfully proceeded under the described condition to afford
the corresponding esters in good yields (4ba, 4bb) with just 2
equivalents of phenols as nucleophiles for the one-pot process.
In addition, much to our delight, benzyl alcohols were also able
to afford the desired products in good to excellent yields (64%－
88%) (4bc, 4bd and 4be).
Table 2. Substrate Scope for the Hydroxycarbonylation of Phenols.
1) SO2F2, Et3N
DMSO, r.t., 2-6 h
CO2H
OH
CO
+
2) Pd(OAc)2, DPPP
NaHCO3, H2O
R
R
3a, b
1
CO2H
CO2H
CO2H
CO2H
CO2H
Table 3. Substrate Scope for the Esterification of Phenols.
H3C
H3CO
F3C
Ph
1) SO2F2, Et3N
DMSO, r.t., 2-6 h
CO2R'
OH
3a, 95%
3b, 93%
3c: p- 76 %
3d: m- 76 %
3e: o- 56 %
3f: p- 56 %
3g: m- 63 %
3h: o- 36 %
3i: p- 97 %
3j: m- 96 %
3k: o- 81 %
CO
+
2) Pd(OAc)2, DPPP
NaHCO3, R'OH
R
R
4 a, b
CO2i-Pr
1
CO2H
CO2H
CO2H
MeO2C
CO2H
OHC
CO2H
CO2Et
CO2Et
CO2Et
CO2Et
Br
NC
Cl
H3C
3l, 81%
3m, 62%
3n, 59%
CO2H
3o, 88%
3p, 91%
H3C
H3CO
Ph
CO2H
4ca: p- 82%
4d: m- 72%
4e: o- 29%
o- 71%c
H3C
H3C
4a 63%
CO2H
Br
4b, 68%
4cb, 54%
CO2H
4f, 81%
3q, 72%
3r, 55%
3s, 95%
3t, 98%
CO2R
H3CO
CO2Et
CO2Et
MeO2C
CO2Et
F3C
[a] Typical procedure for the carbonylation: a mixture of phenol (1, 1.0 mmol),
Et3N (2.0 mmol, 2 eq), DMSO (2.0 mL) was stirred at r.t. charged with a SO2F2
balloon for 2-6 hours before Pd(OAc)2 (3 mol%), DPPP (3 mol%), NaHCO3 (1.5
eq) and H2O (40 eq) were added into the mixture to react for an additional 12
h under CO atmosphere (a CO balloon) at 60 oC. [b] Unless otherwise noticed,
all of the yields are isolated through silica gel chromatography by gradient
elution with dichloromethane and methanol.
NC
4g, 90%
4i: p- 64%
4n, 91%
4ma: Me, 86%
4mb: Et, 85%
4mc: i-Pr, 54%
R
4j: m- 67%
4k: o- 14%
o- 85%c
CO2Et
CO2Et
Cl
CO2Et
CO2Et
CO2Et
O
O
Br
F
4p, 81%c
4q, 83%c
4u, 21%
68%c
4s, 68%
4v, 80%
We were pleased to find that the described method is also
applicable for synthesis of carboxylic esters when alcohols or
phenols were used to take place of water as nucleophiles. As
depicted in Table 3, various phenols were transformed to their
corresponding esters when methanol, ethanol, isopropanol,
phenol and benzyl alcohol were used as nucleophiles. The
esterification procedure scope is also wide, phenols with both
electron-donating group (aromatic groups, alkyl, and ether) and
electron-withdrawing groups (trifluomethyl, cyano, ester, and
halogen) with an ortho-, a meta-, and a para- substituent were
successfully afforded the desired products in moderate to
excellent yield (54-91%). Notably, the position of substituents on
the phenyl rings of phenols has significant influence on the
reaction efficiency. The yields of ortho-substituted products were
typically much lower than the para- or meta-substituted partners
under the same conditions (e.g. 4i, 4j and 4k; 4ca, 4d and 4e).
R
O
O
O
EtO2C
CO2Et
O
O
O
R
Br
4be, 64%f
4ba (R = H), 74%e
4bb (R = OCH3), 65%e
4bc (R = H), 88%f
4bd (R = OCH3), 73%f
4w, 73%d
[a] Typical procedure for the carbonylation: a mixture of phenol (1, 1.0 mmol),
Et3N (2.0 mmol, 2 eq), DMSO (2.0 mL) was stirred at r.t. charged with a SO2F2
balloon for 2-6 hours before Pd(OAc)2 (3 mol %), DPPP (3 mol %), NaHCO3
(1.5 eq), and EtOH (40 eq) were added into the mixture to react for an
additional 12 h under CO atmosphere (a CO balloon) at 60 oC. [b] Unless
otherwise noted, all of the yields are isolated yield. [c] Pd(OAc)2 (5 mmol %),
DPPP (5 mmol%). [d] Pd(OAc)2 (5 mmol %), DPPP (5mmol %), NaHCO3 (3
eq), EtOH (60 eq). [e] Phenol (2 eq) was used for the second step of esters
formation. [f] Benzyl alcohol (5 eq) was used for the second step of esters
formation.
Considering most of the phenolic natural compounds and
bioactive molecules are multi-phenolic and diversifying of them
has attracted significant interests in medicinal chemistry, we also
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Table 4. Pd-catalyzed Esterification of Different Aryl Electrophiles under Mild
applied this protocol for the structure-modification of complicated
natural products diethylstilbestrol 1x and resveratrol 1y
（ Scheme 1） . Not surprisingly, both of these complicated
phenols were transformed to their corresponding multi-esters
smoothly under the developed condition in good to excellent
yield respectively, when the stoichiometry of reagents was
adjusted accordingly (94 % and 80 %), which suggested the
novel carbonylation method has the real potentiality to be widely
applied in organic synthesis.
Conditionsa
Entry
X
Yield (%)b
1
2
3
4
5
6
7
OFs
OTf
Cl
74
65
trace
51
63
0
HO
EtO2C
1) SO2F2, Et3N (4.0 eq)
DMSO, r.t., 3 h
+
CO
(balloon)
2) Pd(OAc)2 (6 mol%)
DPPP (6 mol%)
NaHCO3 (3 eq)
EtOH (60 eq)
OH
OH
CO2Et
Br
1x
4x
Diethylstilbestrol
White Crystal, 94% yield
60 oC, 12 h
M.p. 104-106 o
C
I
CO2Et
OMs
OTs
1) SO2F2, Et3N (5.0 eq)
DMSO, r.t., 3 h
HO
EtO2C
+
CO
(balloon)
2) Pd(OAc)2 (8 mol%)
DPPP (8 mol%)
NaHCO3 (4.5 eq)
EtOH (80 eq)
0
OH
CO2Et
[a] General conditions: Aryl electrophile (0.3 mmol), Pd(OAc)2 (3 mol %),
DPPP (3 mol %), EtOH (40 eq), NaHCO3 (1.5 eq), DMSO (2.5 mL), 60 oC, 12
h. [b] The yields were determined by HPLC using ethyl benzoate (45.5 mg, 0.3
mmol) as theinternal standard (tR = 4.023 min, λmax= 228.7 nm, CH3OH/H2O =
80 : 20 (v / v)).
1y
4y
Resveratrol
60 oC, 12 h
White Solid, 80% yield
M.p. 121-122 o
C
Scheme 1. Esterification of Complex and Multi-Phenolic Natural Molecule.
Gratifyingly, the novel carbonylation catalyst system could be
readily scaled up to gram scale by esterification of 2.48 g of 3-
methoxyphenol (1g) in 79 % yield （ Scheme 2 ） without
deteriorating the efficiency when the reaction time was extended
to 18 h during the second step of the one-pot process. This
finding suggests that this protocol has the potential application
for the direct conversion of phenols to aryl acids or esters in
process chemistry or pharmaceutical and fine chemical industry.
Scheme 2. Scale-up Reaction.
Scheme 3. The plausible Reaction Mechanism.
To compare the esterification of aryl fluorosulfonates to other
common aryl electrophiles under the optimized reaction
conditions, we conducted a series of experiments and measured
the esterifiable yields of these seven aryl electrophiles (Table 4)
under identical reaction conditions. Notably, the aryl
fluorosulfonate was found to be most reactive and effective,
providing the ethyl benzoate 4b in 74 % yield after 12 h (entry 1).
While the benzyl triflate, benzyl iodide and benzyl bromide were
esterified only in 65 %, 63 % and 51 % yield, respectively.
Unfortunately, the benzyl chloride only formed trace amounts of
desired product while benzyl mesylate and benzyl tosylate did
not even provide the desired product in a detectable level.
On the basis previous studies of Palladium-catalyzed
carbonylation of aryl halides, a plausible reaction mechanism
was proposed in the Scheme 3. The aryl fluorosulfonate 2 was
originally generated through the reaction of the phenol 1 and
SO2F2 in the presence of Et3N. Then aryl fluorosulfonate 2
subsequently reacted with [Pd0Ln] species I to generate an
oxidative addition product ArLnPdOSO2F II. Intermediate III was
subsequently formed when the insertion of CO to intermediate II
occurred. The following nucleophilic attack of ROH (R= H, alkyl,
aryl) to Intermediate III provided the target product aromatic
carboxylic acid or aromatic ester together with the formation of
intermediate IV simutaniously. With the assistance of a base, the
intermediate IV loses a H+ along with a reductive elimination to
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regenerate the active [Pd0Ln] species I and to start a new
catalytic cycle thereafter. However, we envision that the main
by-product would be phenols or ethers when the oxidative
addition product ArLnPdOSO2F II don’t undergo through the
process of the insertion of CO but proceed a direct nucleophilic
attack to phenyl group. Indeed, in some cases using benzyl
alcohol as a nucleophile, the formation of the corresponding
benzyl ether as a by-product was confirmed.
SO2F2 gas was introduced into the stirring reaction mixture by slow
bubbling through
a SO2F2 balloon (about 5.5 equiv) at the room
temperature for 2-6 h. The reaction was monitored by TLC. After the
phenol was completely consumed, Pd(OAc)2 (6.75 mg, 3 mol%), DPPP
(12.4 mg, 3 mol%), additional 2.0 mL DMSO, NaHCO3 (126 mg, 1.5
equiv ) and alcohol (40 equiv) or phenol (2.0 equiv) or benzyl alcohol (5.0
eq) were added into the reaction mixture. Then the solution was saturated
with CO by bubbling a stream of gas (balloon) before allowed to stir at 60
oC under CO atmosphere (balloon) for 12 h. Upon the aryl fluorosulfates
had been consumed, the reaction mixture was neutralized with 1 M HCl to
adjust the pH to 5 to 7. After that, the solution was extracted with
dichloromethane (3 × 10 mL). The combined organic layers were washed
with brine, dried over anhydrous Na2SO4, and concentrated to dryness.
The residue was purified by gradient elution through silica gel
chromatography using a mixture of ethyl acetate and hexanes from 2.5%
EtOAc/Hexanes to 20% EtOAc/Hexanes to afford the desired esters 4.
Conclusions
In summary, we have developed a novel procedure for direct
dehydroxylative converting phenols to their corresponding
arylcarboxylic acids and esters through Pd-catalyzed
carbonylative insertion of carbon monoxide in the present of
water or alcohols (phenols) as nucleophiles. The reported
reactions proceeded with mild condition and high efficiency.
Moreover, this practical method, taking advantages of the
abundant and inexpensive supply of sulfuryl fluoride (SO2F2),
[1,1'-biphenyl]-4-carboxylic acid (3a). White solid, 188 mg, 0.95 mmol,
o
1
95% yield. M.p. 227-228 C. H NMR (500 MHz, DMSO-d6) δ 13.00 (brs,
1H), 8.02 (d, J = 8.0 Hz, 2H), 7.79 (d, J = 8.0 Hz, 2H), 7.73 (d, J = 6.5 Hz,
2H), 7.50 (t, J = 6.5 Hz, 2H), 7.42 (t, J = 6.5 Hz, 1H).
Benzoic acid (3b). White solid, 113 mg, 0.93 mmol, 93% yield. M.p.
121-122 oC. 1H NMR (400 MHz, DMSO-d6) δ 12.98 (brs, 1H), 7.95 (d, J =
7.1 Hz, 2H), 7.61 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.5 Hz, 2H).
carbon monoxide (CO) and phenols (ArOH), provides
a
significant attractive option for the assemble of structurally
ubiquitous and widely used carboxylic acid derivatives.
4-Methylbenzoic acid (3c). White solid, 103 mg, 0.76 mmol, 76% yield.
M.p. 181-182 oC. 1H NMR (400 MHz, DMSO-d6) δ 12.81 (brs, 1H), 7.83 (d,
J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H).
Experimental Section
3-Methylbenzoic acid (3d). White solid, 103 mg, 0.76 mmol, 76% yield.
M.p. 112-114 oC. 1H NMR (400 MHz, DMSO-d6) δ 12.85 (brs, 1H), 7.76-
7.73 (m, 2H), 7.43 (d, J =7.5 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 2.36 (s, 3H).
2-Methylbenzoic acid (3e). White solid, 76 mg, 0.56 mmol, 56% yield.
M.p. 103-104 oC. 1H NMR (500 MHz, DMSO-d6) δ 12.67 (brs, 1H), 7.69 (d,
J = 8.0 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.12- 7.10 (m, 2H), 2.37 (s, 3H).
4-Methoxybenzoic acid (3f). White solid, 85 mg, 0.56 mmol, 56% yield.
M.p. 184-185 oC. 1H NMR (400 MHz, DMSO-d6) δ 12.62 (brs, 1H), 7.89 (d,
J = 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 3.81 (s, 3H).
General procedures for the synthesis of aryl carboxylic acids.
Phenol (1.0 mmol, 1.0 equiv), Et3N (202.38 mg, 2.0 mmol, 2.0 equiv)
and 2.0 mL DMSO were added to an over-dried 25 mL reaction flask
equipped with a stirring bar and covered with a plastic stopper before the
SO2F2 gas was introduced into the stirring reaction mixture by slow
bubbling through
a SO2F2 balloon (about 5.5 equiv) at the room
temperature for 2-6 h. The reaction was monitored by TLC. After the
phenol was completely consumed, Pd(OAc)2 (6.75 mg, 3 mol%), DPPP
(12.4 mg, 3 mol%), additional 2.0 mL DMSO, NaHCO3 (126 mg, 1.5
equiv ) and H2O (0.72 mL, 40 equiv) were added into the reaction mixture.
Then the solution was saturated with CO by bubbling a stream of gas
(balloon) before allowed to stir at 60 oC under CO atmosphere (balloon)
for 12 h. Upon the aryl fluorosulfates had been consumed, the reaction
mixture was acidified with 1 M HCl to adjust the pH to 1 to 2. After that,
the solution was extracted with dichloromethane (3× 10 mL). The
combined organic layers were washed with brine, dried over anhydrous
Na2SO4, and concentrated to dryness. The residue was purified by
gradient elution through silica gel chromatography using a mixture of
methanol and dichloromethane from 1% MeOH/CH2Cl2 to 5%
MeOH/CH2Cl2 to afford the desired acids 3.
3-Methoxybenzoic acid (3g). White solid, 96 mg, 0.63 mmol, 63% yield.
M.p. 107-108 oC. 1H NMR (500 MHz, DMSO-d6) δ 12.97 (brs, 1H), 7.53 (d,
J =7.7 Hz, 1H), 7.44 (s, 1H), 7.41 (t, J =7.8 Hz, 1H), 7.18 (d, J = 8.3 Hz,
1H), 3.80 (s, 3H).
3-Methoxybenzoic acid (3h). White solid, 55 mg, 0.36 mmol, 36%
yield. M.p. 100-102 oC. 1H NMR (500 MHz, DMSO-d6) δ 12.60 (brs, 1H),
7.65 (d, J =7.5 Hz, 1H), 7.47 (t, J =7.5 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H),
6.98 (t, J = 7.5 Hz, 1H), 3.80 (s, 3H).
4-(Trifluoromethyl)benzoic acid (3i). White solid, 184 mg, 0.97 mmol,
o
1
97% yield. M.p. 219-220 C. H NMR (500 MHz, DMSO-d6) δ 13.51 (brs,
1H), 8.12 (d, J = 8.1 Hz, 2H), 7.83 (d, J = 8.1 Hz, 2H). 19F NMR (471 MHz,
DMSO-d6) δ -61.7 (m, 3F).
3-(Trifluoromethyl)benzoic acid (3j). White solid, 182 mg, 0.96 mmol,
o
1
96% yield. M.p. 105-106 C. H NMR (500 MHz, DMSO-d6) δ 13.46 (brs,
1H), 8.21 (d, J = 7.5 Hz, 1H), 8.16 (s, 1H), 7.95 (d, J = 6.7 Hz, 1H), 7.75-
7.72 (m, 1H). 19F NMR (471 MHz, DMSO-d6) δ -61.5 (m, 3F).
General procedures for the synthesis of aryl carboxylic esters.
2-(Trifluoromethyl)benzoic acid (3k). White solid, 154 mg, 0.81 mmol,
o
1
Phenol (1.0 mmol, 1.0 equiv), Et3N (202.38 mg, 2.0 mmol, 2.0 equiv)
and 2.0 mL DMSO were added to an over-dried 25 mL reaction flask
equipped with a stirring bar and covered with a plastic stopper before the
81% yield. M.p. 111-112 C. H NMR (500 MHz, DMSO-d6) δ 13.67 (brs,
1H), 7.81 (d, J = 7.0 Hz, 2H), 7.73-7.69 (m, 2H). 19F NMR (471 MHz,
DMSO-d6) δ -58.2 (m, 3F).
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4-Bromobenzoic acid (3l). White solid, 163 mg, 0.81 mmol, 81% yield. 1H), 7.39 (t, J = 8.5 Hz, 1H), 7.26-7.23 (m, 2H), 4.36 (q, J = 7.1 Hz, 2H),
M.p. 254-255 oC. 1H NMR (500 MHz, DMSO-d6) δ 13.42 (brs, 1H), 8.00 (d, 2.60 (s, 3H), 1.40 (t, J = 7.1 Hz, 3H).
J = 8.5 Hz, 2H), 7.84 (d, J = 8.5 Hz, 2H).
Isopropyl 4-methylbenzoate (4cb). Light yellow oil, 96 mg, 0.54 mmol,
4-Cyanobenzoic acid (3m). White solid, 91 mg, 0.62 mmol, 62% yield. 54% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for
M.p. 221-222 oC. 1H NMR (400 MHz, DMSO-d6) δ 13.57 (brs, 1H), 8.07 (d, column chromatography. 1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz,
J = 8.3 Hz, 2H), 7.97(d, J = 8.3 Hz, 2H).
2H), 7.23 (d, J = 8.0 Hz, 2H), 5.24 (hept, J = 6.2 Hz, 1H), 2.41 (s, 3H),
3-(Methoxycarbonyl)benzoic acid (3n). White solid, 106 mg, 0.59 1.36 (d, J = 6.3 Hz, 6H).
mmol, 59% yield. M.p. 193-194 oC. 1H NMR (500 MHz, DMSO-d6) δ 13.36
Ethyl 4-methoxybenzoate (4f). Light yellow oil, 146 mg, 0.81 mmol,
81% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for
(brs, 1H), 8.47 (s, 1H), 8.19-8.16 (m, 2H), 7.67-7.64 (m, 1H), 3.88 (s, 3H).
3-Formylbenzoic acid (3o). White solid, 132 mg, 0.88 mmol, 88% yield. column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.9 Hz,
o
1
M.p. 173-175 C. H NMR (400 MHz, DMSO-d6) δ 13.40 (brs, 1H), 10.09 2H), 6.91 (d, J = 8.9 Hz, 2H), 4.34 (q, J = 7.2 Hz, 2H), 3.85 (s, 3H), 1.38 (t,
(s, 1H), 8.44 (s, 1H), 8.23 (d, J = 7.6 Hz, 1H), 8.13 (d, J = 7.6 Hz, 1H), J = 7.2 Hz, 3H).
7.73 (t, J = 7.6 Hz, 1H).
Ethyl 3-methoxybenzoate (4g). Light yellow oil, 162 mg, 0.90 mmol,
2-Chlorobenzoic acid (3p). White solid, 142 mg, 0.91 mmol, 91% yield. 90% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for
M.p. 139-140 oC. 1H NMR (500 MHz, DMSO-d6) δ 13.42 (brs, 1H), 7.78 (d, column chromatography. 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 7.7 Hz,
J = 7.8 Hz, 1H), 7.52-7.49 (m, 2H), 7.43- 7.40 (m, 1H).
1H), 7.56 (s, 1H), 7.33 (t, J = 8.0 Hz, 1H), 7.09 (dd, J1 = 8.0 Hz, J2 = 2.5
2-Bromobenzoic acid (3q). White solid, 145 mg, 0.72 mmol, 72% yield. Hz, 1H), 4.37 (q, J = 7.2 Hz, 2H), 3.85 (s, 3H), 1.39 (t, J = 7.2 Hz, 3H).
M.p. 147-149 oC. 1H NMR (400 MHz, DMSO-d6) δ 13.44 (brs, 1H), 7.74-
Ethyl 4-(trifluoromethyl)benzoate (4i). Light yellow oil, 140 mg, 0.64
7.70 (m, 2H), 7.48-7.40 (m, 2H).
mmol, 64% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent
3,4-Dimethylbenzoic acid (3r). White solid, 83 mg, 0.55 mmol, 55% for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.16 (d, J = 8.0
yield. M.p. 165-166 oC. 1H NMR (400 MHz, DMSO-d6) δ 12.71 (brs, 1H), Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 4.42 (q, J = 7.1 Hz, 2H), 1.42 (t, J = 7.1
7.71 (s, 1H), 7.66 (d, J = 7.8 Hz, 1H), 7.24 (d, J = 7.8 Hz, 1H), 2.27 (s, 3H), Hz, 3H). 19F NMR (376 MHz, CDCl3) δ -63.1 (s, 3F).
2.26 (s, 3H).
Ethyl 3-(trifluoromethyl)benzoate (4j). Light yellow oil, 146 mg, 0.67
1-Naphthoic acid (3s). White solid, 163 mg, 0.95 mmol, 95% yield. M.p. mmol, 67% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent
161-163 oC. 1H NMR (500 MHz, DMSO-d6) δ 13.14 (brs, 1H), 8.88 (d, J = for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.31 (s, 1H),
8.5 Hz, 1H), 8.15 (d, J = 7.2 Hz, 2H), 8.01 (d, J = 8.0 Hz, 1H), 7.64 (t, J = 8.23 (d, J = 7.8 Hz, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.58 (t, J = 7.8 Hz, 1H),
7.2 Hz, 1H), 7.60-7.57 (m, 2H).
2-Naphthoic acid (3t). White solid, 169 mg, 0.98 mmol, 98% yield. M.p. CDCl3) δ -62.8 (s, 3F).
4.42 (q, J = 7.2 Hz, 2H), 1.42 (t, J = 7.2 Hz, 3H). 19F NMR (376 MHz,
182-183 oC. 1H NMR (500 MHz, DMSO-d6) δ 13.08 (brs, 1H), 8.61 (s, 1H),
Ethyl 2-(trifluoromethyl)benzoate (4k). Light yellow oil, 185 mg, 0.85
8.11 (d, J = 8.1 Hz, 1H), 8.02-8.00 (m, 3H), 7.65 (t, J = 7.8 Hz, 1H), 7.60 (t, mmol, 85% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent
J = 7.5 Hz, 1H).
for column chromatography. 1H NMR (400 MHz, CDCl3) δ 7.79-7.73 (m,
Ethyl [1,1'-biphenyl]-4-carboxylate (4a). White solid, 143 mg, 0.63 2H), 7.63-7.58 (m, 2H), 4.40 (q, J = 7.2 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H).
o
mmol, 63% yield. M.p. 92-94 C. Petroleum ether / ethyl acetate = 40 : 1 19F NMR (376 MHz, CDCl3) δ -59.4 (s,3F).
(v / v) as eluent for column chromatography. 1H NMR (500 MHz, CDCl3) δ
Methyl 4-cyanobenzoate (4ma). White solid, 138 mg, 0.86 mmol, 86%
8.12 (d, J = 7.0 Hz, 2H), 7.67 (d, J = 7.2 Hz, 2H), 7.63 (d, J = 7.0 Hz, 2H), yield. M.p. 63-64 oC. Petroleum ether / ethyl acetate = 10 : 1 (v / v) as
7.47- 7.46 (m, 2H), 7.41-7.40 (m, 1H), 4.41 (q, J = 6.5 Hz, 2H), 1.42 (t, J = eluent for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J
6.5 Hz, 3H).
= 8.5 Hz, 2H), 7.74 (d, J = 8.5 Hz, 2H), 3.96 (s, 3H).
Ethyl benzoate (4b). Light yellow oil, 102 mg, 0.68 mmol, 68% yield.
Ethyl 4-cyanobenzoate (4mb). White solid, 149 mg, 0.86 mmol, 85%
Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column yield. M.p. 52-54 oC. Petroleum ether / ethyl acetate = 10 : 1 (v / v) as
chromatography. 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.2 Hz, 2H), eluent for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J
7.55 (t, J = 7.5 Hz, 1H), 7.44 (t, J = 7.5 Hz, 2H), 4.38 (q, J = 7.2 Hz, 2H), = 8.4 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H), 4.41 (q, J = 7.2 Hz, 2H), 1.40 (t, J
1.40 (t, J = 7.2 Hz, 3H).
= 7.2 Hz, 3H).
Ethyl 4-methylbenzoate (4ca). Light yellow oil, 134 mg, 0.82 mmol,
Isopropyl 4-cyanobenzoate (4mc). White solid, 102 mg, 0.54 mmol,
o
82% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for 54% yield. M.p. 49-51 C. Petroleum ether / ethyl acetate = 10 : 1 (v / v)
column chromatography. 1H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 8.1 Hz, as eluent for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.13
2H), 7.23 (d, J = 8.1 Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 2.41 (s, 3H), 1.39 (t, (d, J = 8.5 Hz, 2H), 7.73 (d, J = 8.5 Hz, 2H), 5.23 (hept, J = 6.2 Hz, 1H),
J = 7.1 Hz, 3H).
1.38 (d, J = 6.2 Hz, 6H).
Ethyl 3-methylbenzoate (4d). Light yellow oil, 118 mg, 0.72 mmol,
Ethyl methyl isophthalate (4n). White oil, 189 mg, 0.91 mmol, 91%
72% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column
column chromatography. 1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 9.2 Hz chromatography. 1H NMR (400 MHz, CDCl3) δ 8.66 (s, 1H), 8.20 (t, J =
2H), 7.37-7.30 (m, 2H), 4.38 (q, J = 7.2 Hz, 2H), 2.41 (s, 3H), 1.40 (t, J = 6.6 Hz, 2H), 7.50 (t, J = 7.8 Hz, 1H), 4.39 (q, J = 7.2 Hz, 2H), 3.93 (s, 3H),
7.2 Hz, 3H).
1.39 (t, J = 7.2 Hz, 3H).
Ethyl 2-methylbenzoate (4e). Light yellow oil, 116 mg, 0.71 mmol,
Ethyl 2-chlorobenzoate (4p). Light yellow oil, 150 mg, 0.81 mmol, 81%
71% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column
column chromatography. 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, chromatography. 1H NMR (400 MHz, CDCl3) δ 7.80 (dd, J 1 = 7.6 Hz, J 2
=
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1.5 Hz, 1H), 7.44-7.34 (m, 2H), 7.29 (td, J = 7.6 Hz, J = 1.5 Hz, 1H), literature. 1H NMR (500 MHz, CDCl3) δ 8.12 (d, J = 7.3 Hz, 2H), 7.61 (d, J
1
2
4.39 (q, J = 7.2 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H).
= 7.9 Hz, 1H), 7.58 (t, J = 7.3 Hz, 1H), 7.52 (d, J = 7.7 Hz, 1H), 7.46 (t, J =
Ethyl 2-bromobenzoate (4q). Light yellow oil, 189 mg, 0.83 mmol, 83% 7.6 Hz, 2H), 7.35 (t, J = 7.5 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 5.47 (s, 2H).
yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column
chromatography. 1H NMR (400 MHz, CDCl3) δ 7.70 (dd, J 1 = 7.5 Hz, J 2
Diethyl 4,4'-(hex-3-ene-3,4-diyl)(E)-dibenzoate (4x). White crystal,
346 mg, 0.91 mmol, 91% yield. M.p. 104-106 oC. Petroleum ether / ethyl
=
1.8 Hz, 1H), 7.65 (dd, J 1 = 7.8 Hz, J 2 = 1.2 Hz, 1H), 7.36 (td, J 1 = 7.5 Hz, acetate = 20 : 1 (v / v) as eluent for column chromatography. 1H NMR
J 2 = 1.2 Hz, 1H), 7.31 (td, J 1 = 7.5 Hz, J 2 = 1.8 Hz, 1H), 4.40 (q, J = 7.2 (500 MHz, CDCl3) δ 8.06 (d, J = 8.1 Hz, 4H), 7.29 (d, J = 8.1 Hz, 4H), 4.40
Hz, 2H), 1.41 (t, J = 7.2 Hz, 3H).
(q, J = 7.2 Hz, 4H), 2.13 (q, J = 7.4 Hz, 4H), 1.41 (t, J = 7.1 Hz, 6H), 0.76
Ethyl 1-naphthoate (4s). Light yellow oil, 156 mg, 0.8 mmol, 80% yield. (t, J = 7.4 Hz, 6H). 13C (126 MHz, CDCl3) 166.6, 147.2, 139.2, 129.5,
Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column 128.8, 128.7, 60.9, 28.4, 14.4, 13.1. ESI-MS HRMS calculated for
chromatography. 1H NMR (400 MHz, CDCl3) δ 8.95 (d, J = 8.7 Hz, 1H), C24H29O4 [M+1]+ 381.2066, found 381.2059.
8.20 (d, J = 7.2 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H),
7.63 (t, J = 7.2 Hz, 1H), 7.56-7.49 (m, 2H), 4.50 (q, J = 7.2 Hz, 2H), 1.48 (t, 317 mg, 0.8 mmol, 80 % yield. M.p. 121-122 oC. Petroleum ether / ethyl
J = 7.2 Hz, 3H).
acetate = 5 : 1 (v / v) as eluent for column chromatography. 1H NMR (500
Diethyl (E)-5-(4-(ethoxycarbonyl)styryl)isophthalate (4y). White solid,
Ethyl 2-fluorobenzoate (4u). Light yellow oil, 114 mg, 0.68 mmol, 68% MHz, CDCl3) δ 8.58 (s, 1H), 8.38 (s, 2H), 8.06 (d, J = 8.2 Hz, 2H), 7.60 (d,
yield. Petroleum ether / ethyl acetate = 60 : 1 (v / v) as eluent for column J = 8.3 Hz, 2H), 7.28-7.27 (m, 2H), 4.44 (q, J = 7.2 Hz, 4H), 4.39 (q, J =
chromatography. 1H NMR (400 MHz, CDCl3) δ 7.93 (td, J 1 = 7.6 Hz, J 2
=
7.2 Hz, 2H), 1.46-1.40 (m, 9H). 13C (126 MHz, CDCl3) 166.3, 165.7, 140.9,
1.2 Hz, 1H), 7.53-7.48 (m, 1H), 7.19 (t, J = 7.6 Hz, 1H),7.15-7.10 (m, 1H), 137.6, 131.6, 131.5, 130.1, 130.0, 129.9, 129.8, 129.0, 126.6, 61.5, 61.0,
4.39 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H). 19F NMR (376 MHz, 14.4, 14.4. ESI-MS HRMS calculated for C23H25O6 [M+1]+ 397.1651,
CDCl3) δ -109.7 (m, 1F).
found 397.1642.
Ethyl benzo[d][1,3]dioxole-5-carboxylate (4v). Light yellow oil, 156
mg, 0.8 mmol, 80% yield. Petroleum ether / ethyl acetate = 40 : 1 (v / v) as
eluent for column chromatography. 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J
= 8.3 Hz, 1H), 7.46 (s, 1H), 6.82 (d, J = 8.3 Hz, 1H), 6.02 (s, 2H), 4.33 (q,
J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H).
Acknowledgements
This work was supported by Wuhan University of Technology
and the Fundamental Research Funds for the Central
Universities (175220008 to W.-Y. Fang), we are grateful to
professor K. B. Sharpless (the Scripps Research Institute) for
helpful discussion and advisory.
Diethyl isophthalate (4w). White oil, 162 mg, 0.73 mmol, 73% yield.
Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column
chromatography. 1H NMR (500 MHz, CDCl3) δ 8.67 (s, 1H), 8.20 (d, J =
7.8 Hz, 2H), 7.50 (t, J = 7.7 Hz, 1H), 4.39 (q, J = 7.2 Hz, 4H), 1.40 (t, J =
7.2 Hz, 6H).
Phenyl benzoate (4ba). White solid, 146 mg, 0.74 mmol, 74% yield.
Petroleum ether / ethyl acetate = 20 : 1 (v / v) as eluent for column
chromatography. M.p. 71-72 oC. 1H NMR (500 MHz, CDCl3) δ 8.23 (d, J =
7.7 Hz, 2H), 7.66 (t, J = 7.5 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H), 7.46 (t, J =
7.8 Hz, 2H), 7.30 (t, J = 7.5 Hz, 1H), 7.24 (d, J = 8.1 Hz, 2H). 13C (126
MHz, CDCl3) 165.2, 151.0, 133.6, 130.2, 129.6, 129.5, 128.6, 125.9,
121.8.
Keywords: sulfuryl fluoride • phenols • aryl fluorosulfonates •
arylcarboxylic acids • arylcarboxylic esters
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4-Methoxyphenyl benzoate (4bb). White solid, 148 mg, 0.65 mmol,
o
65% yield. M.p. 86-88 C. Petroleum ether / ethyl acetate = 10 : 1 (v / v)
as eluent for column chromatography. 1H NMR (500 MHz, CDCl3) δ 8.21
(d, J = 7.7 Hz, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H), 7.15
(d, J = 8.7 Hz, 2H), 6.95 (d, J = 8.7 Hz, 2H), 3.83 (s, 3H).
Benzyl benzoate (4bc). Colorless oil, 188 mg, 0.88 mmol, 88% yield.
Petroleum ether / ethyl acetate = 40 : 1 (v / v) as eluent for column
chromatography. The NMR data is identical to that reported in literature.
1H NMR (500 MHz, CDCl3) δ 8.12 (d, J = 8.0 Hz, 2H), 7.58 (t, J = 7.5 Hz,
1H), 7.50-7.36 (m, 7H), 5.41 (s, 2H).
[2] a) H. Kolbe, Ann. Chem. Pharm., 1860, 113, 125-127. b) M. B.
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4-Methoxybenzyl benzoate (4bd). Colorless oil, 177 mg, 0.73 mmol,
73% yield. Petroleum ether / ethyl acetate = 20 : 1 (v / v) as eluent for
column chromatography. The NMR data is identical to that reported in
literature. 1H NMR (500 MHz, CDCl3) δ 8.08 (d, J = 7.5 Hz, 2H), 7.56 (t, J
= 7.5 Hz, 1H), 7.45-7.40 (m, 4H), 6.94 (d, J = 8.6 Hz, 2H), 5.32 (s, 2H),
3.82 (s, 3H).
[3] For recent reviews, see: a) L. J. Gooßen, N. Rodríguez, K. Gooßen, Angew.
Chem. Int. Ed. 2008, 47, 3100; Angew. Chem. 2008, 120, 3144. b) K.
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[13] During our investigation for the transformation of phenols to the
arylcarboxylic amides with amines as nucleophiles instead of OH or
alcohols under similar condition, an interesting unexpected
transformation happened, the details of that reaction and the mechanism
will be reported in the due course.
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Wan-Yin Fang, Jing Leng, Hua-Li Qin*
Page No. – Page No.
SO2F2 Mediated One-Pot Synthesis of
Arylcarboxylic Acids and Esters from
Phenols via a Pd-Catalyzed Carbon
Monoxide Insertion
Text for Table of Contents : A practical method for direct dehydroxylative converting phenols to their corresponding arylcarboxylic
acids and esters was developed. This protocol utilized the abundant and inexpensive supply of sulfuryl fluoride (SO2F2), carbon
monoxide (CO) and phenols (ArOH), to provide a significant attractive option for the synthesis of structurally ubiquitous and widely
used carboxylic acid derivatives with wide scope and functional group tolerability.
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