Note

pubs.acs.org/joc

Cobalt- and Nickel-Catalyzed Carboxylation of Alkenyl and Sterically

Hindered Aryl Triflates Utilizing CO2
Keisuke Nogi, Tetsuaki Fujihara,* Jun Terao, and Yasushi Tsuji*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto
615-8510, Japan
*
S Supporting Information

ABSTRACT: A highly efficient cobalt-catalyzed reductive carboxylation

reaction of alkenyl trifluoromethanesulfonates (triflates) has been
developed. By employing Mn powder as a reducing reagent under 1 atm
pressure of CO2 at room temperature, diverse alkenyl triflates can be
converted to the corresponding α,β-unsaturated carboxylic acids. More-
over, the carboxylation of sterically hindered aryl triflates proceeds
smoothly in the presence of a nickel or cobalt catalyst.

C arbon dioxide (CO2) is considered an ideal C1-synthon

for organic synthesis because of its nontoxicity, low cost,
and availability as a renewable resource.1 Therefore, the
Scheme 1. Reductive Carboxylation of Alkenyl and Sterically
Hindered Aryl Electrophiles

development of new catalytic methods enabling chemical

fixation of CO2 with concomitant C−C bond formation is
considered an important current challenge.2 In this regard,
reductive catalytic carboxylation reactions of organic electro-
philes with CO2 have been studied intensively.3−5 Catalytic
carboxylation of aryl bromides with a palladium catalyst was
reported by the Martin group in 2009 with an excess amount of
pyrophoric Et2Zn as a reducing reagent.3b In 2012, we reported
the first catalytic carboxylation of less reactive aryl chlorides as
well as alkenyl chlorides with a nickel catalyst.4a The reaction
proceeded under 1 atm pressure of CO2 at room temperature
employing easy-to-handle Mn powder as a reducing reagent.
Martin and co-workers have also developed nickel-catalyzed
reductive carboxylation reactions of various organic halides and
esters.5
Even the carboxylation reactions of aryl chlorides afford a The reaction of an alkenyl triflate 1a was examined with Mn
wide variety of products with high functional group tolerance; powder (1.5 equiv) as a reducing reagent under 1 atm pressure
the previous paper4a posed the following two significant of CO2 at room temperature (Table 1). The yield of α,β-
problems: (1) only three simple alkenyl chlorides (without unsaturated carboxylic acid (2a) was determined by gas
other functionalities) were employed as substrates, but chromatographic (GC) analysis after derivatization to the
reactivity of more easily accessible alkenyl triflates was not corresponding methyl ester (2a-Me). First, the carboxylation
examined (Scheme 1a, left); (2) sterically hindered ortho- reaction of 1a was carried out employing NiBr2(L1) (5 mol %,
substituted aryl chlorides, even 2-chlorotoluene, did not afford L1 = 2,2′-bipyridine) as a catalyst in the presence of additional
carboxylated products with only low conversions of substrates L1 (15 mol %) and tetraethylammonium iodide (Et4NI, 10 mol
(Scheme 1b, left). %) in 1,3-dimethyl-2-imidazolidinone (DMI) solvent, i.e. under
In this paper, to compensate for the former results,4a we the optimal reaction conditions of the former carboxylation of
focus on the reactivity of alkenyl and aryl trifluoromethane- alkenyl chlorides.4a In the reaction, 2a-Me was obtained in 43%
sulfonates (triflates) as substrates. They are easily prepared GC yield (entry 1), but ca. 30% of diene was afforded as the
from the corresponding ketones, aldehydes, or phenol homocoupled product of 1a. To improve the selectivity, we
derivatives and are often employed in synthetic organic switched the catalyst to a cobalt complex that showed excellent
chemistry as useful reagents.6 Herein, we describe highly catalytic activity for the carboxylation of propargyl acetates with
efficient reductive carboxylations of alkenyl triflates (Scheme CO2.4b Use of CoI2(L1) showed low catalytic activity in both
1a, right) and sterically hindered aryl triflates (Scheme 1b,
right) employing Mn powder as a reducing reagent in the Received: October 5, 2015
presence of a cobalt or nickel catalyst.7,8

© XXXX American Chemical Society A DOI: 10.1021/acs.joc.5b02307

J. Org. Chem. XXXX, XXX, XXX−XXX
The Journal of Organic Chemistry Note

Table 1. Optimization of the Reaction Conditions with 1aa Table 2. Cobalt-Catalyzed Carboxylation of Alkenyl
Triflatesa,b

entry metal catalyst solvent yield of 2a-Me (%)b

1c NiBr2(L1) DMI 43
2 CoI2(L1) DMI 10
3 CoI2(L1) DMA 23
4 CoI2(L2) DMA 76
5 CoI2(L3) DMA 86 (79)d
6 CoI2(PPh3)2 DMA 0
7 CoI2(dppe) DMA 0
8e CoI2(L3) DMA 32
9f CoI2(L3) DMA 0
10 Without catalyst DMA 0
a
Reaction conditions: 1a (0.25 mmol), metal catalyst (5.0 mol %), Mn
powder (1.5 equiv) in solvent (0.50 mL), at room temperature for 20
h. bDetermined by GC analysis using tridecane as an internal standard.
c
L1 (15 mol %) and Et4NI (10 mol %) were added. dIsolated yield of
2a as the carboxylic acid. eZn (1.5 equiv) was used in place of Mn.
f
Without Mn. a
Reaction conditions; 1 (0.25 mmol), CoI2(L3) (5.0 mol %), Mn
powder (1.5 equiv) in DMA (0.50 mL) at room temperature for 20 h.
b
Isolated yield. cDetermined by GC and GC-MS analysis after
methylesterification.

furnished the carboxylated product 4a in 84% isolated yield

in the presence of NiI2(PPh3)2 (5.0 mol %) and additional PPh3
DMI and DMA solvents, but no homocoupling reaction of 1a (10 mol %) at room temperature (Table 3). Other 2-
occurred (entries 2 and 3). The yield of 2a-Me was increased
substantially with 1,10-phenanthroline (L2) as the ligand (entry Table 3. Cobalt- and Nickel-Catalyzed Carboxylation of
4). Finally, CoI2(L3) (L3 = 2,9-dimethyl-1,10-phenanthroline) Sterically Hindered Aryl Triflatesa,b
as the catalyst afforded 2a-Me in 86% yield and the
corresponding carboxylic acid 2a was isolated in 79% yield
(entry 5).9 The catalyst in situ prepared from CoI2 and L3 also
worked well and afforded the product in 86% yield. Phosphine
ligands were not effective at all (entries 6 and 7). In place of
Mn, Zn powder afforded the product in low yield (entry 8).
The cobalt catalyst and Mn powder were indispensable for this
carboxylation reaction (entries 9 and 10).
Under the optimal reaction conditions (Table 1, entry 5),
carboxylation of various alkenyl triflates was carried out (Table
2). Ester (2c), indole (2f), and furan (2g) moieties were well
tolerated under the reaction conditions.10 Importantly, the
triflate moiety was selectively carboxylated even in the presence
of p-toluenesulfonate (2d) and chloro (2j) functionalities
which could be potentially reactive under the reductive
carboxylation conditions. Conjugated alkenyl triflates (1h−j)
a
were converted to the corresponding carboxylic acids (2h−j) in Reaction conditions: 3 (0.25 mmol), nickel or cobalt catalyst (5.0
moderate to high yields. A seven-membered cyclic substrate mol %), Mn powder (1.5 equiv) in DMA (0.50 mL) at 40 °C for 20 h.
b
(1k) also afforded the α,β-unsaturated carboxylic acid 2k in Isolated yield. cNiI2(PPh3)2 (5.0 mol %) was used. dPPh3 (10 mol %)
was added, room temperature. eNiI2(L3) (5.0 mol %) was used, at
75% yield. An alkenyl triflate 1l prepared from the
room temperature. fCoI2(L3) (5.0 mol %) was used. gCoI2(L3) (10
corresponding aldehyde gave the product 2l in moderate mol %) was used.
yield. Unfortunately, 1m having an exo-methylene moiety gave
a trace amount of product owing to extensive side reactions. An
estrone-based alkenyl triflate (1n) furnished the product 2n in substituted aryl triflates (3b−d) provided the corresponding
22% yield due to a preferential homocoupling reaction (41% benzoic acids (4b−d) in good to excellent yields. It is
yield) of 1n. noteworthy that bulky substituents such as tert-butyl and TBS
As mentioned above, ortho-substituted aryl chlorides could (tert-butyldimethylsilyl) moieties did not hamper the carbox-
not be carboxylated in our previous paper.4a Even 2- ylation reaction. As for more sterically hindered 2,6-
chlorotoluene did not give the desired carboxylation product. disubstituted aryl triflates, 2,4,6-trimethylphenyl triflate 3e
So, we changed the substrate from the aryl chloride to 2- only afforded the carboxylated product (4e) in 15% yield
methylphenyl triflate 3a. To our delight, 3a successfully even at elevated temperature (60 °C) in the presence of the
B DOI: 10.1021/acs.joc.5b02307
J. Org. Chem. XXXX, XXX, XXX−XXX
The Journal of Organic Chemistry Note

nickel catalyst. In contrast, a cobalt catalyst CoI2(L3) was found 0 °C. The resulting mixture was warmed to room temperature and
to be more active and successfully afforded 4e in 77% yield at stirred for 2 h. The reaction was quenched by adding H2O (20 mL).
40 °C. More sterically demanding 2-methyl-6-(trimethylsilyl)- The organic layer was washed with sat. NaHCO3 aq. and brine and
phenyl triflate (3f) was also carboxylated to 4f in 66% yield dried over MgSO4. After filtration and removal of volatiles, the residue
with a higher catalyst loading (10 mol %). However, 2,6- was purified with silica gel chromatography using hexane as an eluent.
Ethyl 4-(Trifluoromethanesulfonyloxy)cyclohex-3-ene-1-carbox-
diisopropylphenyl triflate (3g) did not give the product (4g). ylate (1c). Colorless oil (7.0 mmol scale, 1.0 g, 3.4 mmol, 49%); 1H
Regarding less hindered substrates, phenyl triflate afforded NMR (500 MHz, CDCl3): δ 5.78−5.76 (m, 1H), 4.16 (q, J = 7.2 Hz,
benzoic acid in 54% yield utilizing NiI2(PPh3)2 (5.0 mol %) and 2H), 2.62−2.57 (m, 1H), 2.48−2.40 (m, 4H), 2.17−2.11 (m, 1H),
PPh3 (10 mol %) as the catalyst. 1.97−1.89 (m, 1H), 1.27 (t, J = 7.2 Hz, 3H). 13C NMR (126 MHz,
In conclusion, we explored highly efficient reductive CDCl3): δ 173.9, 148.4, 118.5 (q, JC−F = 320.1 Hz), 116.9, 60.8, 37.8,
carboxylations of various alkenyl triflates employing a cobalt 26.6, 26.1, 25.0, 14.1. ESI-HRMS (m/z): [M + Na] calcd for
catalyst and Mn powder as a reducing reagent under 1 atm C10H13F3O5SNa, 325.0328; found, 325.0322.
pressure of CO2 at room temperature. Furthermore, the 4-[4-(Trifluoromethanesulfonyloxy)cyclohex-3-en-1-yl]phenyl 4-
carboxylation of sterically hindered 2-substituted and 2,6- Methylbenzene-1-sulfonate (1d). White solid (5.0 mmol scale, 1.6
g, 3.3 mmol, 66%); mp 93−95 °C; 1H NMR (500 MHz, CDCl3): δ
disubstituted aryl triflates proceeded smoothly with a nickel or
7.72 (d, J = 8.2 Hz, 2H), 7.32 (d, J = 7.9 Hz, 2H), 7.13 (d, J = 8.5 Hz,
cobalt catalyst.

■
2H), 6.95−6.92 (m, 2H), 5.84−5.82 (m, 1H), 2.86−2.81 (m, 1H),
2.56−2.24 (m, 7H), 2.06−2.01 (m, 1H), 1.94−1.86 (m, 1H). 13C
EXPERIMENTAL SECTION NMR (126 MHz, CDCl3): δ 148.8, 148.2, 145.3, 143.4, 132.5, 129.7,
General Methods and Materials. DMA and DMI were distilled 128.5, 127.9, 122.5, 118.5 (q, JC−F = 320.1 Hz), 117.8, 38.1, 31.4, 29.5,
with CaH2 and stored over activated MS-4A. Mn powder (≥99%) was 27.6, 21.7. ESI-HRMS (m/z): [M + Na]+ calcd for C20H19F3O6S2Na,
purchased from Sigma-Aldrich and stored under a nitrogen 499.0467; found, 499.0456.
atmosphere. Zn powder was activated by washing with HCl aq. and 3,4-Dihydronaphthalen-1-yl Trifluoromethanesulfonate (1i).8c
stored under a nitrogen atmosphere. Unless otherwise noted, materials Colorless oil (7.0 mmol scale, 1.9 g, 6.7 mmol, 96%); 1H NMR
obtained from commercial suppliers were used without further (500 MHz, CDCl3): δ 7.36−7.33 (m, 1H), 7.28−7.24 (m, 2H), 7.18−
purification. IR spectra were obtained on an FT-IR spectrometer. 1H 7.16 (m, 1H), 6.01 (t, J = 4.7 Hz, 1H), 2.87 (t, J = 8.2 Hz, 2H), 2.51
and 13C NMR spectra were measured with a spectrometer (500 or 400 (td, J = 8.2, 4.7 Hz, 2H). 13C NMR (126 MHz, CDCl3): δ 146.4,
MHz). The 1H NMR chemical shifts are reported relative to 136.2, 129.2, 128.7, 127.8, 126.9, 121.2, 118.6 (q, JC−F = 320.4 Hz),
tetramethylsilane (TMS, 0.00 ppm), acetone-d6 (2.05 ppm), or 117.7, 26.9, 22.3.
DMSO-d6 (2.50 ppm). The 13C NMR chemical shifts are reported 7-Chloro-3,4-dihydronaphthalen-1-yl Trifluoromethanesulfonate
relative to CDCl3 (77.0 ppm), acetone-d6 (29.0 ppm), or DMSO-d6 (1j). Colorless oil (2.8 mmol scale, 0.55 g, 1.8 mmol, 63%); 1H NMR
(39.5 ppm). GC-MS data were recorded on a low-resolution EI-MS (500 MHz, CDCl3): δ 7.31 (d, J = 1.8 Hz, 1H), 7.23 (dd, J = 8.1, 2.0
(quadrupole). High-resolution mass spectra were obtained with EI- Hz, 1H), 7.11 (d, J = 7.9 Hz, 1H), 6.08 (t, J = 4.9 Hz, 1H), 2.83 (t, J =
HRMS (magnetic sector), ESI-HRMS (Orbitrap), APCI-HRMS 8.1 Hz, 2H), 2.52 (td, J = 8.2, 4.8 Hz, 2H). 13C NMR (126 MHz,
(Orbitrap), and MALDI-HRMS (Orbitrap). GC analysis was carried CDCl3): δ 145.2, 134.4, 132.9, 130.2, 129.0 (two peaks overlap
out using a gas chromatographic analyzer equipped with a capillary absolutely, confirmed with the HMQC and HMBC spectra), 121.4,
column (0.25 mm i.d. × 30 m). UV/vis spectra were recorded with a 119.2, 118.6 (q, JC−F = 320.4 Hz), 26.2, 22.3. APCI-HRMS (m/z):
spectrophotometer. Column chromatography was carried out on silica [M−H]− calcd for C11H7ClF3O3S, 310.9762; found, 310.9760.
gel (spherical, neutral, 40−50 μm or 63-210 μm). TLC analyses were 1-Cyclohepten-1-yl Trifluoromethanesulfonate (1k).11 Pale brown
performed on commercial glass plates bearing a 0.25 mm layer of silica oil (6.0 mmol scale, 0.52 g, 2.1 mmol, 35%); 1H NMR (500 MHz,
gel. Alkenyl triflates 1a−b,11 1f−g,12 1h,13 1m,8c and 1n,14 as well as CDCl3): δ 5.88 (t, J = 6.4 Hz, 1H), 2.53−2.51 (m, 2H), 2.17−2.14 (m,
aryl triflates 3a,15 3b,16 3c,15 3d,17 3e,18 and 3g18 were prepared 2H), 1.74−1.61 (m, 6H). 13C NMR (126 MHz, CDCl3): δ 153.1,
according to the literature procedures. CoI 2(L1), CoI2(L2),
123.1, 118.6 (q, JC−F = 320.1 Hz), 33.2, 29.9, 26.3, 24.8, 24.7.
CoI2(PPh3)2, CoI2(dppe), NiBr2(L1), and NiI2(PPh3)2 were also
Cyclohexylidenemethyl Trifluoromethanesulfonate (1l). Pale
prepared according to the literature procedures.4b,19
yellow oil (5.0 mmol scale, 0.40 g, 1.6 mmol, 33%); 1H NMR (500
Preparation of CoI2(L3) and NiI2(L3). CoI2(L3) was prepared
MHz, CDCl3): δ 6.38 (s, 1H), 2.28−2.26 (br m, 2H), 2.07−2.05 (br
according to a published method for CoBr2(L3).20 A 50 mL Schlenk
flask was dried with a heating gun under vacuum. The flask was m, 2H), 1.59−1.57 (br m, 6H). 13C NMR (126 MHz, CDCl3): δ
charged with CoI2 (0.31 g, 1.0 mmol), 2,9-dimethyl-1,10-phenanthro- 133.8, 127.7, 118.7 (q, JC−F = 321.1 Hz), 29.8, 27.5, 26.4, 26.04, 26.00.
line (L3, 0.23 g, 1.1 mmol), and ethanol (5 mL) under an Ar EI-HRMS (m/z): [M]+ calcd for C8H11F3O3S, 244.0381; found,
atmosphere. The resulting solution was stirred at 80 °C for 2 h. A light 244.0374.
green solid was precipitated and isolated by filtration. The solid was Preparation of 6-Methylcyclohex-1-en-1-yl Trifluoro-
filtered, washed with ethanol and hexane subsequently, and dried in methanesulfonate (1e). 11 A mixture of potassium bis-
vacuo. The desired complex was obtained in 83% yield (0.43 g, 0.83 (trimethylsilyl)amide (KHMDS, 10 mL of 0.5 M toluene solution)
mmol) and used without further purification. Stable under 250 °C; and THF (25 mL) was cooled to −78 °C under an Ar atmosphere. To
UV−vis (CH3CN) λmax, nm: 212, 272, 320, 390 (sh), 670 (br). Anal. the solution was added dropwise the solution of 2-methylcyclohex-
Calcd for C14H12CoI2N2·1/2CH3CH2OH: C, 33.12; H, 2.78; N, 5.15. anone (4.0 mmol) in THF (5.0 mL), and the resulting mixture was
Found: C, 33.07; H, 2.53; N, 5.41. MALDI-HRMS (m/z): [M−I]+ stirred at −78 °C for 1 h. Then, PhNTf2 (5.0 mmol) was added in one
calcd for C14H12CoIN2, 393.93717; found, 393.93678. portion, and the reaction mixture was allowed to warm to room
NiI2(L3) was prepared by the same procedure (0.50 mmol scale, temperature. After stirring for 6 h, H2O (10 mL) was added, and the
0.23 g, 0.45 mmol, 89%). Light brown solid; mp 220−230 °C (dec); resulting mixture was extracted with Et2O (2 × 20 mL). The combined
UV−vis (CH3CN) λmax, nm: 208, 248, 276, 360. Anal. Calcd for organic layer was washed with brine and dried over MgSO4. After
C14H12NiI2N2·1/2CH3CH2OH: C, 33.13; H, 2.78; N, 5.15. Found: C, filtration and removal of volatiles, purification of the residue by silica
33.03; H, 2.56; N, 5.40. MALDI-HRMS (m/z): [M−I]+ calcd for gel chromatography using hexane as an eluent gave 1e (colorless oil,
C14H12IN2Ni, 392.93932; found, 392.93976. 0.53 g, 2.1 mmol, 53%). 1H NMR (500 MHz, CDCl3): δ 5.73 (td, J =
General Procedure for Preparation of Alkenyl Triflates. To a 4.1, 1.2 Hz, 1H), 2.58−2.51 (m, 1H), 2.19−2.15 (m, 2H), 1.96−1.90
mixture of ketone (10 mmol) and 2-chloropyridine (11 mmol) in (m, 1H), 1.70−1.43 (m, 3H), 1.14 (d, J = 6.7 Hz, 3H). 13C NMR (126
CH2Cl2 (20 mL), the solution of Tf2O (12 mmol) in CH2Cl2 (10 mL) MHz, CDCl3): δ 153.4, 118.6 (q, JC−F = 320.1 Hz), 118.2, 32.4, 31.5,
was added dropwise at 0 °C and the mixture was stirred for 30 min at 24.5, 19.2, 17.8.

C DOI: 10.1021/acs.joc.5b02307
J. Org. Chem. XXXX, XXX, XXX−XXX
The Journal of Organic Chemistry Note

Preparation of 2-Methyl-6-(trimethylsilyl)phenyl Trifluoro- C10H13O4, 197.0819; found, 197.0815. IR (neat): 3100−2800 (br),
methanesulfonate (3f). A mixture of 2-bromo-6-methylphenol (10 1720.5, 1683.9, 1645.3, 1379.1, 1249.9, 1174.7, 1141.9, 1089.8, 1033.9,
mmol), TMSCl (10 mmol), and THF (20 mL) was cooled to 0 °C 856.4, 763.8 cm−1.
under an Ar atmosphere. To the solution was added dropwise 4-{4-[(4-Methylbenzenesulfonyl)oxy]phenyl}cyclohex-1-ene-1-
triethylamine (10 mmol), and the resulting solution was allowed to carboxylic Acid (2d). White solid (62 mg, 67%); mp 238−240 °C; 1H
warm to room temperature. After stirring for 2 h, white precipitate was NMR (500 MHz, DMSO−D6): δ 12.17 (br s, 1H), 7.74 (d, J = 8.2 Hz,
filtered off and the filtrate was concentrated under vacuum to afford 2H), 7.47 (d, J = 7.9 Hz, 2H), 7.27 (d, J = 8.9 Hz, 2H), 6.95−6.90 (m,
the crude mixture of (2-bromo-6-methylphenoxy)trimethylsilane. The 3H), 2.78−2.72 (m, 1H), 2.42−2.19 (m, 7H), 1.86−1.84 (m, 1H),
crude mixture was placed in 100 mL round bottled flask and diluted 1.68−1.60 (m, 1H). 13C NMR (126 MHz, DMSO−D6): δ 167.9,
with THF (20 mL) under Ar atmosphere. The mixture was cooled to 147.3, 145.7, 145.3, 138.1, 131.6, 130.2, 130.1, 128.3, 128.1, 121.8,
−78 °C and n-BuLi in hexane (1.65 M, 9.1 mL, 15 mmol) was added 37.7, 32.8, 28.9, 24.4, 21.1. ESI-HRMS (m/z): [M−H]− calcd for
slowly. The whole mixture was stirred for 1h at −78 °C. Then, Tf2O C20H19O5S, 371.0959; found, 371.0953. IR (neat): 3100−2800 (br),
(15 mmol) was added via syringe and the resulting solution was 1716.7, 1681.9, 1674.2, 1558.5, 1541.1, 1506.4, 1456.3, 1373.3, 1278.8,
allowed to warm to room temperature. After stirring for 1 h, the 1197.8, 1174.7, 1153.4, 1089.8, 864.1, 750.3, 723.3 cm−1.
reaction was quenched by adding H2O and the mixture was extracted 6-Methylcyclohex-1-ene-1-carboxylic Acid (2e).8d White solid (25
with Et2O (2 × 20 mL). The combined organic layer was subsequently mg, 70%); 1H NMR (500 MHz, CDCl3): δ 7.10 (t, J = 4.0 Hz, 1H),
washed with NaHCO3 aq. and brine, and dried over MgSO4. After 2.72−2.66 (m, 1H), 2.28−2.12 (m, 2H), 1.67−1.55 (m, 4H), 1.11 (d, J
filtration and removal of all volatiles, purification of the residue by = 7.0 Hz, 3H). 13C NMR (126 MHz, CDCl3): δ 173.1, 142.2, 134.7,
silica gel chromatography using hexane as an eluent gave 3f (Colorless 29.5, 27.5, 26.2, 20.2, 17.0.
oil, 1.7 g, 5.3 mmol, 53%). 1H NMR (500 MHz, CDCl3): δ 7.39 (d, J = 3-(1-Methyl-1H-indol-3-yl)cyclohex-1-ene-1-carboxylic Acid (2f).
6.7 Hz, 1H), 7.29−7.25 (m, 2H), 2.38 (s, 3H), 0.38 (s, 9H). 13C NMR White solid (53 mg, 83%); mp 166−168 °C; 1H NMR (500 MHz,
(126 MHz, CDCl3): δ 151.1, 134.8, 134.5, 133.7, 131.4, 127.9, 118.6 CDCl3): δ 10.89 (brs, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.29−7.28 (m,
(q, JC−F = 319.8 Hz), 17.3, 0.1. ESI-HRMS (m/z): [M−H]− calcd for 2H), 7.24−7.21 (m, 1H), 7.11 (t, J = 7.3 Hz, 1H), 6.76 (s, 1H), 3.88
C11H14F3O3SSi, 311.0390; found, 311.0392. (brs, 1H), 3.71 (s, 3H), 2.38−2.35 (m, 2H), 2.06−2.01 (m, 1H),
A Procedure for Carboxylation of 1a (Table 1, entry 5). A 20 1.83−1.75 (m, 2H), 1.71−1.66 (m, 1H). 13C NMR (126 MHz,
mL Schlenk flask was charged with Mn powder (21 mg, 0.38 mmol) CDCl3): δ 173.3, 144.7, 137.2, 129.8, 126.7, 126.4, 121.7, 118.9, 118.9,
and dried with a heating-gun under vacuum. Then, the flask was 116.9, 109.3, 33.4, 32.6, 29.2, 23.9, 20.4. ESI-HRMS (m/z): [M−H]−
charged with CoI2(L3) (6.5 mg, 0.013 mmol). The flask was evacuated calcd for C16H16NO2, 254.1187; found, 254.1185. IR (neat): 3100−
and refilled with CO2. This sequence was repeated five times. Then, 2800 (br), 1716.6, 1670.3, 1626.0, 1558.5, 1541.1, 1506.4, 1473.6,
DMA (0.50 mL) and 1a (59 μL, 0.25 mmol) were added via airtight 1456.3, 1288.5, 1257.6, 808.2, 733.0 cm−1.
syringes, and the resulting mixture was stirred at room temperature for 3-(5-Methylfuran-2-yl)cyclohex-1-ene-1-carboxylic Acid (2g). Yel-
20 h. After the reaction, tridecane (50 μL, 0.21 mmol) as an internal low solid (41 mg, 80%); mp 97−99 °C; 1H NMR (500 MHz, CDCl3):
standard, Et2O (5 mL), and 1 M HCl aq. (3 mL) were added to the δ 7.16−7.14 (m, 1H), 5.88 (d, J = 3.1 Hz, 1H), 5.86 (d, J = 3.1 Hz,
reaction mixture. After stirring for 10 min, the organic layer was 1H), 3.62−3.59 (m, 1H), 2.33−2.29 (m, 2H), 2.26 (s, 3H), 2.00−1.95
separated, dried over MgSO4, and filtrated. Then, methanol (1 mL) (m, 1H), 1.86−1.79 (m, 1H), 1.77−1.70 (m, 1H), 1.69−1.61 (m, 1H).
and TMSCHN2 (2.0 M in Et2O, 0.5 mL, 1.0 mmol) were added to the 13
C NMR (126 MHz, CDCl3): δ 173.0, 154.4, 151.0, 141.3, 130.6,
resulting solution, and it was stirred for 10 min. The yield of 2a-Me 105.9 (two peaks overlap absolutely, confirmed with the HMQC and
was determined by GC analysis. HMBC spectra), 35.8, 27.1, 23.8, 20.2, 13.5. ESI-HRMS (m/z): [M−
Representative Procedure for the Carboxylation of Alkenyl H]− calcd for C12H13O3, 205.0870; found, 205.0867. IR (neat): 3100−
Triflates (1b−n) and Aryl Triflates (3a−g). A 20 mL Schlenk flask 2800 (br), 1683.9, 1635.6, 1558.5, 1508.3, 1417.7, 1288.5, 1020.3,
was charged with Mn powder (21 mg, 0.38 mmol) and dried with a 788.9 cm−1.
heating gun under vacuum. Then, the flask was charged with CoI2(L3) 3,4-Dihydronaphthalene-2-carboxylic Acid (2h).22 Pale yellow
(6.5 mg, 0.013 mmol). The flask was evacuated and refilled with CO2. solid (34 mg, 78%); 1H NMR (500 MHz, DMSO-d6): δ 12.45 (br s,
This sequence was repeated five times. Then, DMA (0.50 mL) and 1 1H), 7.47 (s, 1H), 7.32 (d, J = 7.0 Hz, 1H), 7.28−7.21 (m, 3H), 2.81
(0.25 mmol) were added via airtight syringes, and the resulting (t, J = 8.4 Hz, 2H), 2.47 (t, J = 8.4 Hz, 2H). 13C NMR (126 MHz,
mixture was stirred at room temperature for 20 h. After the reaction, 1 DMSO-d6): δ 168.0, 136.5, 135.4, 132.3, 129.9, 129.3, 128.3, 127.5,
M HCl aq. (3 mL) and Et2O (5 mL) were added, and the whole 126.7, 26.9, 21.9.
solution was stirred at room temperature for 10 min. The mixture was 3,4-Dihydronaphthalene-1-carboxylic Acid (2i).23 Pale yellow
extracted with Et2O (5 mL × 5). The collected organic layer was solid (23 mg, 53%); 1H NMR (500 MHz, CDCl3): δ 7.91 (d, J =
combined and dried over anhydrous MgSO4. After removal of 7.6 Hz, 1H), 7.41 (t, J = 4.7 Hz, 1H), 7.26−7.16 (m, 3H), 2.78 (t, J =
volatiles, the residue was purified by silica gel chromatography using 7.8 Hz, 2H), 2.47−2.43 (m, 2H). 13C NMR (126 MHz, CDCl3): δ
hexane/acetone (6/1, v/v) as an eluent. 171.9, 143.0, 136.2, 130.4, 129.9, 127.7, 127.5, 126.6, 126.2, 27.4, 23.7.
4-Phenylcyclohex-1-ene-1-carboxylic Acid (2a).4b White solid (40 7-Chloro-3,4-dihydronaphthalene-1-carboxylic Acid (2j). White
mg, 79%); 1H NMR (500 MHz, CDCl3): δ 7.33−7.30 (m, 2H), 7.23− solid (24 mg, 45%); mp 189−191 °C; 1H NMR (500 MHz, acetone-
7.21 (m, 4H), 2.83−2.77 (m, 1H), 2.58−2.51 (m, 2H), 2.38−2.31 (m, d6): δ 8.03 (s, 1H), 7.38 (t, J = 4.9 Hz, 1H), 7.21 (app. d, J = 1.2 Hz,
2H), 2.07−2.03 (m, 1H), 1.80−1.72 (m, 1H). 13C NMR (126 MHz, 2H), 2.76 (t, J = 7.9 Hz, 2H), 2.44 (td, J = 8.0, 5.0 Hz, 2H). 13C NMR
CDCl3): δ 172.9, 145.8, 141.8, 129.7, 128.5, 126.8, 126.3, 39.0, 33.9, (126 MHz, acetone-d6): δ 166.3, 142.4, 135.1, 132.9, 131.5, 128.98,
29.3, 24.4. 128.96, 127.1, 126.0, 26.4, 23.2. ESI-HRMS (m/z): [M−H]− calcd for
4-tert-Butylcyclohex-1-ene-1-carboxylic Acid (2b).21 White solid C11H8ClO2, 207.0218; found, 207.0215. IR (neat): 3100−2800 (br),
(34 mg, 74%); 1H NMR (500 MHz, CDCl3): δ 7.14−7.12 (m, 1H), 1716.7, 1683.9, 1558.5, 1541.1, 1506.4, 1489.1, 1473.6, 1456.3, 1174.7,
2.52−2.48 (m, 1H), 2.31−2.25 (m, 1H), 2.16−2.08 (m, 1H), 2.00− 889.2, 835.2, 814.0, 715.6 cm−1.
1.90 (m, 2H), 1.31−1.25 (m, 1H), 1.18−1.10 (m, 1H), 0.89 (s, 9H). Cyclohep-1-ene-1-carboxylic Acid (2k).21 Pale yellow solid (26 mg,
13
C NMR (126 MHz, CDCl3): δ 173.0, 143.0, 129.6, 43.2, 32.1, 27.7, 75%); 1H NMR (500 MHz, CDCl3): δ 7.35 (t, J = 6.7 Hz, 1H), 2.52
27.1, 25.2, 23.5. (dd, J = 5.5, 5.5 Hz, 2H), 2.32 (dd, J = 11.3, 6.4 Hz, 2H), 1.81−1.76
4-(Ethoxycarbonyl)cyclohex-1-ene-1-carboxylic Acid (2c). White (m, 2H), 1.58−1.51 (m, 4H). 13C NMR (126 MHz, CDCl3): δ 173.8,
solid (38 mg, 76%); mp 97−98 °C; 1H NMR (500 MHz, CDCl3): δ 147.3, 135.9, 32.0, 29.0, 36.9, 26.1, 25.6.
7.12−7.10 (br m, 1H), 4.18−4.14 (m, 2H), 2.59−2.45 (m, 4H), 2.29− 2-Cyclohexylideneacetic Acid (2l).24 White solid (15 mg, 43%); 1H
2.22 (m, 1H), 2.13−2.08 (m, 1H), 1.76−1.68 (m, 1H), 1.27 (t, J = 7.2 NMR (500 MHz, CDCl3): δ 5.63 (s, 1H), 2.83 (t, J = 5.8 Hz, 2H),
Hz, 3H). 13C NMR (126 MHz, CDCl3): δ 175.0, 172.3, 140.2, 129.3, 2.22 (t, J = 6.1 Hz, 2H), 1.68−1.59 (m, 6H). 13C NMR (126 MHz,
60.6, 38.2, 28.0, 24.7, 23.1, 14.2. ESI-HRMS (m/z): [M−H]− calcd for CDCl3): δ 172.2, 166.8, 112.5, 38.3, 30.1, 28.7, 27.9, 26.2.

D DOI: 10.1021/acs.joc.5b02307
J. Org. Chem. XXXX, XXX, XXX−XXX
The Journal of Organic Chemistry Note

Product 2n. White solid (17 mg, 22%); mp 231−233 °C; 1H NMR acknowledges financial support from a Grant-in-Aid for
(500 MHz, CDCl3): δ 7.21 (d, J = 8.5 Hz, 1H), 6.97−6.96 (m, 1H), Young Scientists (A) (No. 25708017) from JSPS.

■
6.72 (dd, J = 8.7, 2.6 Hz, 1H), 6.64 (d, J = 2.7 Hz, 1H), 3.78 (s, 3H),
2.96−2.85 (m, 2H), 2.42−2.27 (m, 4H), 2.17−2.11 (m, 1H), 1.94− REFERENCES
1.90 (m, 1H), 1.75−1.60 (m, 4H), 1.51−1.42 (m, 1H), 0.97 (s, 3H).
13
C NMR (126 MHz, CDCl3): δ 169.8, 157.5, 146.4 (two peaks (1) (a) New and Future Developments in Catalysis: Activation of
overlap absolutely, confirmed with the HMQC and HMBC spectra), Carbon Dioxide; Suib, S. L., Ed.; Elsevier: Waltham, 2013. (b) Carbon
137.8, 132.7, 126.1, 113.9, 111.5, 55.8, 55.2, 46.0, 44.2, 37.1, 34.7, 31.9, Dioxide as Chemical Feedstock; Aresta, M., Ed.; Wiley-VCH: Weinheim,
29.6, 27.7, 26.4, 16.0. ESI-HRMS (m/z): [M−H]− calcd for C20H23O3, 2010.
311.1653; found, 311.1656. IR (neat): 3100−2800 (br), 2358.9, (2) For selected reviews, see: (a) Zhang, L.; Hou, Z. Chem. Sci. 2013,
1674.2, 1600.9, 1498.7, 1427.3, 1282.7, 1053.1, 964.4, 902.7, 808.2, 4, 3395−3403. (b) Tsuji, Y.; Fujihara, T. Chem. Commun. 2012, 48,
781.2, 731.0 cm−1. 9956−9964. (c) Martin, R.; Kleij, A. W. ChemSusChem 2011, 4, 1259−
2-Methylbenzoic Acid (4a).25 White solid (29 mg, 84%); 1H NMR 1263. (d) Cokoja, M.; Bruckmeier, C.; Rieger, B.; Herrmann, W. A.;
(500 MHz, CDCl3): δ 8.08 (d, J = 7.9 Hz, 1H), 7.46−7.43 (m, 1H), Kühn, F. E. Angew. Chem., Int. Ed. 2011, 50, 8510−8537. (e) Huang,
7.30−7.27 (m, 2H), 2.67 (s, 3H). 13C NMR (126 MHz, CDCl3): δ K.; Sun, C.-L.; Shi, Z.-J. Chem. Soc. Rev. 2011, 40, 2435−2452.
173.6, 141.4, 133.0, 132.0, 131.6, 128.4, 125.9, 22.2. (f) Riduan, S. N.; Zhang, Y. Dalton Trans. 2010, 39, 3347−3357.
2-Phenylbenzoic Acid (4b).26 White solid (34 mg, 69%); 1H NMR (3) For reductive carboxylations of aryl halides employing Et2Zn as a
(500 MHz, CDCl3): δ 7.94 (d, J = 7.9 Hz, 1H), 7.55 (td, J = 7.6, 1.2 reducing reagent, see: (a) Tran-Vu, H.; Daugulis, O. ACS Catal. 2013,
Hz, 1H), 7.43−7.32 (m, 7H). 13C NMR (126 MHz, CDCl3): δ 173.3, 3, 2417−2420. (b) Correa, A.; Martin, R. J. Am. Chem. Soc. 2009, 131,
143.4, 141.0, 132.1, 131.2, 130.7, 129.3, 128.4, 128.1, 127.3, 127.2. 15974−15975.
2-tert-Butylbenzoic Acid (4c).27 Pale yellow solid (34 mg, 77%); (4) (a) Fujihara, T.; Nogi, K.; Xu, T.; Terao, J.; Tsuji, Y. J. Am. Chem.
1
H NMR (500 MHz, CDCl3): δ 7.53−7.48 (m, 2H), 7.40 (td, J = 7.8, Soc. 2012, 134, 9106−9109. (b) Nogi, K.; Fujihara, T.; Terao, J.; Tsuji,
1.4 Hz, 1H), 7.25 (td, J = 7.5, 1.1 Hz, 1H), 1.48 (s, 9H). 13C NMR Y. Chem. Commun. 2014, 50, 13052−13055.
(126 MHz, CDCl3): δ 178.2, 148.2, 131.7, 130.5, 129.0, 127.1, 125.5, (5) (a) Wang, X.; Liu, Y.; Martin, R. J. Am. Chem. Soc. 2015, 137,
36.0, 31.4. 6476−6479. (b) Moragas, T.; Cornella, J.; Martin, R. J. Am. Chem. Soc.
2-(tert-Butyldimethylsilyl)benzoic Acid (4d). Carboxylation of 3d 2014, 136, 17702−17705. (c) Liu, Y.; Cornella, J.; Martin, R. J. Am.
was carried out on 0.50 mmol scale. White solid (0.11 g, 93%); mp Chem. Soc. 2014, 136, 11212−11215. (d) Correa, A.; León, T.; Martin,
106−108 °C; 1H NMR (400 MHz, CDCl3): δ 8.03 (d, J = 7.2 Hz, R. J. Am. Chem. Soc. 2014, 136, 1062−1069. (e) León, T.; Correa, A.;
1H), 7.71 (d, J = 7.2 Hz, 1H), 7.52 (t, J = 7.2 Hz, 1H), 7.44 (t, J = 7.2 Martin, R. J. Am. Chem. Soc. 2013, 135, 1221−1224.
Hz, 1H), 0.95 (s, 9H), 0.34 (s, 6H). 13C NMR (100 MHz, CDCl3): δ (6) For selected reviews, see: (a) Chassaing, S.; Specklin, S.; Weibel,
174.6, 140.3, 137.1, 135.9, 131.3, 130.3, 128.6, 27.8, 18.3, −2.4. ESI- J.-M.; Pale, P. Tetrahedron 2012, 68, 7245−7273. (b) Ritter, K.
HRMS (m/z): [M−H]− calcd for C13H19O2Si, 235.1160; found, Synthesis 1993, 735−762.
235.1157. IR (neat): 3200−2800 (br), 1683.9, 1562.3, 1417.7, 1275.0, (7) Although the catalytic carboxylation of alkenyl triflates employing
1259.5, 1149.6, 1114.91, 921.9, 839.0, 823.6, 808.2, 771.5, 736.8, 707.9 CO2 to α,β-unsaturated carboxylic acids was first developed as
cm−1. electrochemical reactions,8 these were not efficient synthetic methods
2,4,6-Trimethylbenzoic Acid (4e).28 White solid (32 mg, 77%); 1H and the substrate scope was limited.
NMR (500 MHz, CDCl3): δ 6.88 (s, 2H), 2.42 (s, 6H), 2.29 (s, 3H). (8) For electrochemical carboxylation reactions of alkenyl triflates,
13
C NMR (126 MHz, CDCl3): δ 175.9, 140.1, 136.2, 129.3, 128.8, see: (a) Senboku, H.; Kanaya, H.; Tokuda, M. Synlett 2002, 140−142.
21.1, 20.3. (b) Senboku, H.; Kanaya, H.; Fujimura, Y.; Tokuda, M. J. Electroanal.
2-Methyl-6-(trimethylsilyl)benzoic Acid (4f). White solid (35 mg, Chem. 2001, 507, 82−88. (c) Senboku, H.; Fujimura, Y.; Kamekawa,
66%); mp 96−98 °C; 1H NMR (500 MHz, CDCl3): δ 7.47 (d, J = 7.3 H.; Tokuda, M. Electrochim. Acta 2000, 45, 2995−3003. (d) Jutand, A.;
Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.25 (d, J = 8.2 Hz, 1H), 2.50 (s, Négri, S. Eur. J. Org. Chem. 1998, 1811−1821. (e) Jutand, A.; Négri, S.
3H), 0.34 (s, 9H). 13C NMR (126 MHz, CDCl3): δ 177.2, 139.4, Synlett 1997, 719−721.
136.9, 135.9, 132.3, 131.5, 129.8, 20.6, 0.1. ESI-HRMS (m/z): [M− (9) Martin and co-workers have found that the use of 2,9-dimethyl-
H]− calcd for C11H15O2Si, 207.0847; found, 207.0842. IR (neat): 1,10-phenanthroline (L3) as a ligand was effective in the nickel-
3100−2800 (br), 1689.6, 1296.2, 1250.0, 1126.4, 879.5, 835.2, 792.7, catalyzed carboxylation of unactivated alkyl halides, sulfonates, and
752.2 cm−1. allyl esters.5b,c

■
(10) When the reaction of 1a was carried out in the presence of
ASSOCIATED CONTENT nitrobenzene, the carboxylation reaction was completely suppressed.
(11) Lim, B.-Y.; Jung, B.-E.; Cho, C.-G. Org. Lett. 2014, 16, 4492−
*
S Supporting Information 4495.
The Supporting Information is available free of charge on the (12) Grundl, M. A.; Kaster, A.; Beaulieu, E. D.; Trauner, D. Org. Lett.
ACS Publications website at DOI: 10.1021/acs.joc.5b02307. 2006, 8, 5429−5432.
1
H NMR and 13C NMR spectra for obtained compounds (13) Konishi, H.; Ueda, T.; Manabe, K. Org. Synth. 2014, 91, 39−51.
(14) Sun, Q.; Jiang, C.; Xu, H.; Zhang, Z.; Liu, L.; Wang, C. Steroids
(PDF) 2010, 75, 936−943.

■ AUTHOR INFORMATION
Corresponding Authors
(15) Qin, L.; Ren, X.; Lu, Y.; Li, Y.; Zhou, J. Angew. Chem., Int. Ed.
2012, 51, 5915−5919.
(16) Wang, J.-Q.; Harvey, R. G. Tetrahedron 2002, 58, 5927−5931.
(17) Peña, D.; Cobas, A.; Pérez, D.; Guitián, E. Synthesis 2002,
*E-mail: [email protected]. 1454−1458.
*E-mail: [email protected]. (18) Zhu, S.; Wang, C.; Chen, L.; Liang, R.; Yu, Y.; Jiang, H. Org.
Notes Lett. 2011, 13, 1146−1149.
The authors declare no competing financial interest. (19) Yamamoto, K. Bull. Chem. Soc. Jpn. 1954, 27, 501−505.

■
(20) Al-Noaimi, M.; Awwadi, F. F.; Haddad, S. F.; Talib, W. H.;
ACKNOWLEDGMENTS Jodeh, S.; Radi, S.; Hadda, T. B.; Abdoh, M.; Naveen, S.; Lokanath, N.
K.; Warad, I. J. Mol. Struct. 2015, 1086, 153−160.
This work was supported by a Grant-in-Aid for Scientific (21) Vitnik, V. D.; Ivanović, M. D.; Vitnik, Ž . J.; Đorđević, J. B.;
Research (A) from MEXT, Japan. K.N. is grateful for a Ž ižak, Ž . S.; Juranić, Z. D.; Juranić, I. O. Synth. Commun. 2009, 39,
Research Fellowship of JSPS for Young Scientists. T.F. 1457−1471.

E DOI: 10.1021/acs.joc.5b02307
J. Org. Chem. XXXX, XXX, XXX−XXX
The Journal of Organic Chemistry Note

(22) Biscoe, M. R.; Breslow, R. J. Am. Chem. Soc. 2005, 127, 10812−
10813.
(23) Sun, S.; Yu, J.-T.; Jiang, Y.; Cheng, J. J. Org. Chem. 2015, 80,
2855−2860.
(24) Bellassoued, M.; Mouelhi, S.; Fromentin, P.; Gonzalez, A. J.
Organomet. Chem. 2005, 690, 2172−2179.
(25) Murray, A. T.; Matton, P.; Fairhurst, N. W. G.; John, M. P.;
Carbery, D. R. Org. Lett. 2012, 14, 3656−3659.
(26) Zhu, C.; Zhang, Y.; Kan, J.; Zhao, H.; Su, W. Org. Lett. 2015, 17,
3418−3421.
(27) Gohier, F.; Castanet, A.-S.; Mortier, J. Org. Lett. 2003, 5, 1919−
1922.
(28) Sun, S.; Yu, J.-T.; Jiang, Y.; Cheng, J. Adv. Synth. Catal. 2015,
357, 2022−2026.

F DOI: 10.1021/acs.joc.5b02307
J. Org. Chem. XXXX, XXX, XXX−XXX