Ni-Catalyzed Decarboxylative Cross-Coupling of Potassium Polyfluorobenzoates with Unactivated Phenol and Phenylmethanol Derivatives

Article abstract of DOI:10.1002/adsc.201800729

A Ni-catalyzed decarboxylative cross-coupling of potassium polyfluorobenzoates with unactivated phenol and phenylmethanol derivatives is described. This novel transformation provides a practical and efficient protocol towards the synthesis of important polyfluorobiaryls and polyfluorinated diarylmethanes, and greatly enlarges the range of electrophiles utilized in decarboxylative coupling. Remarkably, preliminary mechanistic studies indicated the essential role of Zn(OAc)₂ might lie in the enhancement of decarboxylation step. (Figure presented.).

Full text of DOI:10.1002/adsc.201800729

Title: Ni-Catalyzed Decarboxylative Cross-Coupling of Potassium
Polyfluorobenzoates with Unactivated Phenol and
Phenylmethanol Derivatives
Authors: Quan Chen, Aizhen Wu, Shengxiang Qin, Meiqi Zeng, Zhiping
Le, Zhaohua Yan, and Hua Zhang
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800729
Link to VoR: http://dx.doi.org/10.1002/adsc.201800729

10.1002/adsc.201800729
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Ni-Catalyzed Decarboxylative Cross-Coupling of Potassium
Polyfluorobenzoates with Unactivated Phenol and
Phenylmethanol Derivatives
Quan Chen,+ Aizhen Wu,+ Shengxiang Qin, Meiqi Zeng, Zhiping Le,* Zhaohua Yan,*
Hua Zhang*
a
College of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031, P. R. China. Email:
zple@ncu.edu.cn; yanzh@ncu.edu.cn; huazhang@ncu.edu.cn
These authors contributed equally to this work.
+
Received: ((will be filled in by the editorial staff))
This paper is dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
transformations including decarboxylative cross-
of potassium polyfluorobenzoates with unactivated phenol coupling.[3] During the past decade, the C–O bond
Abstract. A Ni-catalyzed decarboxylative cross-coupling
and phenylmethanol derivatives is described. This novel
transformation provides a practical and efficient protocol
towards the synthesis of important polyfluorobiaryls and
polyfluorinated diarylmethanes, and greatly enlarges the
range of electrophiles utilized in decarboxylative coupling.
Remarkably, preliminary mechanistic studies indicated the
essential role of Zn(OAc)2 might lie in the enhancement of
decarboxylation step.
functionalization of simpler and less activated
phenol derivatives[4] especially aryl carboxylates
and sulfamates to construct carbon-carbon[5] and
carbon-heteroatom[6]
bonds
has
attracted
considerable attentions. However, to the best of
our knowledge, the decarboxylative cross-
coupling involving aryl carboxylates and
sulfamates as electrophiles has never been
realized (Scheme 1).
Keywords: decarboxylative cross-coupling; C–O bond
functionalization; nickel-catalyzed; phenol derivatives;
polyfluorobiaryls
Previous Work: Aryl Halides and Sulfonates
[TM]
Ar1
Ar2
Ar1
Ar2
+
E
MOOC
E = I, Br, Cl, OTf, OTs, OMs
This Work: Aryl Carboxylates and Sulfamates
Ni(cod)2
PCy3
The biaryl scaffold constitutes the core structure
of a wide variety of naturally occurring and
manmade compounds, such as pharmaceuticals,
agrochemicals, ligands, organic materials etc.[1] In
Fn
R = COtBu, SO2NMe2
Fn
Ar
+
Ar
OR
KOOC
Zn(OAc)2
"Crucial Role"
Polyfluorobiaryls
Abundant & Inexpensive
Substrates
Nickel
Catalysis
Valuable
Products
recent
years,
transition-metal-catalyzed
decarboxylative cross-coupling has emerged as a
significant alternative to traditional cross-
coupling reactions towards biaryls synthesis
(Scheme 1).[2] This method utilizes inexpensive,
highly stable and readily available carboxylic
acids instead of expensive and sensitive
organometallic reagents, and generates CO2
instead of metal halide byproducts. In the past
decade, great progress has been made in the
decarboxylative cross-coupling enabling the use
of various aryl halides including iodides,
bromides and chlorides as electrophiles.
Phenol derivatives are abundant, inexpensive,
highly stable and readily available chemicals.
Activated aryl sulfonates including triflates,
tosylates and mesylates have been employed as
versatile alternatives to aryl halides in various
Scheme 1. Biaryl synthesis via classical decarboxylative
cross-coupling.
Herein, we communicate the decarboxylative
cross-coupling of potassium polyfluorobenzoates
with unactivated phenol and phenylmethanol
derivatives to afford polyfluorobiaryls and
polyfluorinated diarylmethanes via nickel
catalysis under simple reaction conditions.
Remarkably, polyfluorobiaryls find important
application in the fields of medicinal chemistry[7]
and material science[8]. This novel protocol
provides a significant implement to the former
synthetic routes of polyfluorobiaryls such as
Suzuki-Miyaura
cross-coupling
of
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800729
Advanced Synthesis & Catalysis
pentafluorophenylboronic acid[9] and C–H bidentate phosphine ligand (dppf) and N-
arylation of polyfluoroarene[10]
heterocyclic carbene ligand (IPr•HCl) showed
.
We began by investigating the decarboxylative much less or little efficiency. The use of
cross-coupling of 2-naphthyl pivalate 1a with Zn(OAc)2 as additive was crucial to the success of
potassium perfluorobenzoate 2a in the presence of this reaction as only 6% GC yield was obtained in
nickel catalyst. After extensive screening, the best the absence of Zn(OAc)2. The use of other
result was obtained when the reaction was conducted additives such as Cu(OAc)2, AgOAc and ZnCl2
under the conditions consisting of Ni(cod)2 (10 mol%; afforded trace or no product. Ag2CO3 and Cu2O,
cod = 1,5-cyclooctadiene), tricyclohexylphosphine the commonly used additives for decarblyxlative
(PCy3, 20 mol%), and Zn(OAc)2 (1.0 equiv) in cross-coupling were ineffective for this
chexane at 170 oC for 16 h affording the product 3a in transformation. Replacing chexane by toluene
81% GC yield and 76% isolated yield (Table 1). It is afforded lower yield of desired product. No
noteworthy that C–F bonds survived under the product was obtained employing diglyme and
conditions.[11]
DMF as solvent. Lowering the reaction
o
temperature to 150 C led to 52% GC yield while
o
Table 1. Ni-catalyzed decarboxylative cross-coupling of 2a increasing the catalyst loading at 150 C afforded
with 1a: effects of reaction parameters.
69% isolated yield.
F
F
COOK
Table 2. Ni-catalyzed decarboxylative cross-coupling
Ni(cod)2 (10 mol%)
PCy3 (20 mol%)
F
F
F
F
F
OPiv
of potassium polyfluorobenzoates with aryl
+
pivalates.a,b
F
Zn(OAc)2 (1.0 equiv)
chexane, 170 oC, 16 h
F
Ni(cod)2 (10 mol%)
PCy3 (20 mol%)
F
OPiv
COOK
Fn
+
Fn
Ar
1a
2a
3a
Zn(OAc)2 (1.0 equiv)
chexane, 170 oC, 16 h
Ar
Entry Variation from “standard conditions”a Yield[%]b
1
2
3
F
3a, R = H, 76%
1
2
none
81(76)c
R
F
F
F
3d, R = 6-OMe, 69%
3e, R = 7-OMe, 74%
3f, R = 7-NMe2, 61%
3g, R = 6-OTBS, 43%
3h, R = 6-CO2Me, 60%c
3i, R = 6-Pyrazole, 65%
F
F
F
No Ni(cod)2
0
R
F
3
PMe3 instead of PCy3
dppf instead of PCy3
trace
19
F
F
F
3b, R = H, 74%
3c, R = 4-Bn, 66%
4d
5e
6
trace
6
IPrHCl instead of PCy3
No Zn(OAc)2
F
F
F
F
F
F
F
F
F
F
7
8
Cu(OAc)2 instead of Zn(OAc)2
AgOAc instead of Zn(OAc)2
ZnCl2 instead of Zn(OAc)2
Ag2CO3 instead of Zn(OAc)2
Cu2O instead of Zn(OAc)2
toluene instead of chexane
diglyme instead of chexane
DMF instead of chexane
150 oC instead of 170 oC
150 oC instead of 170 oC
0
F
F
F
F
N
trace
trace
6
3k 60%c
3l 55%d
3j 60%
9
F
F
F
Me
F
10
11
12
13
14
15
16f
F
trace
63
F
F
F
3m 46%d
3n 41%d
3o 24%d
a)
0
Reaction conditions:
1
(0.2 mmol),
2
(0.4 mmol),
Ni(cod)2 (0.02 mmol), PCy3 (0.04 mmol), Zn(OAc)2
0
c
o
(0.2 mmol), hexane (3.0 mL), 170 C, 16 h. b) Isolated
52
69c
c)
o
d)
yield. 190 C. toluene/DMA (2.0 mL/0.2 mL), 190
oC.
a) Standard reaction conditions: 1a (0.2 mmol), 2a (0.4
mmol), Ni(cod)2 (0.02 mmol), PCy3 (0.04 mmol),
Furthermore, the reactivity of various C–O
bond electrophiles with 2a was tested under the
standard conditions (see Table S1 in the
Supporting Information). 2-Naphthyl acetate and
benzoate both showed lower reactivity than 2-
naphthyl pivalate. No product was obtained in the
reaction of 2-naphthyl carbonate while the
decarboxylative coupling of 2-naphthyl carbamate
and sulfonmate resulted in lower yields than 2-
naphthyl pivalate. Both naphthalen-2-ol and 2-
methoxynaphthalene were inactive under the
present reaction conditions.
c
o
Zn(OAc)2 (0.2 mmol), hexane (3.0 mL), 170 C, 16 h.
b)
The yield was determined by GC, and calibrated
n
c)
using dodecane as internal standard. Isolated yield
in parenthesis. dppf (0.02 mmol). NaOtBu (0.04
d)
e)
mmol). f) Ni(cod)2 (0.04 mmol), PCy3 (0.08 mmol).
The effect of alteration to the “standard
conditions” is listed in Table 1. When no catalyst
presented, essentially no reaction occurred.
Trimethylphosphine (PMe3) as ligand afforded
only trace amount of desired product. The use of
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800729
Advanced Synthesis & Catalysis
With the optimized reaction conditions in hand,
Phenyl pivalates showed much less reactivity
a variety of aryl pivalates
1 was subjected to this affording trace amount of desired products under
decarboxylative cross-coupling reaction (Table 2). present reaction conditions. Similar phenomenon
1-Naphthyl pivalate 1b showed similar reactivity was observed in other reports on transformation
as 2-naphthyl pivalate. Generally, naphthyl of inert C–O bonds.[12] Switching the substrates
pivalates bearing with electron-donating and from phenyl pivalates to phenyl sulfamates, no
electron-withdrawing groups worked well under product was obtained under standard conditions.
the standard conditions affording the desired Employing
both
DPPF
(1,1'-
polyfluorobiaryls in moderate to good yields. Bis(diphenylphosphino)ferrocene) and BINAP
Naphthyl pivalates bearing benzyl, methoxy, (2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl) as
dimethylamino and pyrazole groups could be well ligand allowed this decarboxylative cross-
tolerated under standard reaction conditions. In a coupling process to occur smoothly while trace or
similar manner, 9-phenanthrenyl pivalate 1j was low yield was obtained utilizing DPPF or BINAP
also suitable substrate. Ester and silyl ether group alone as ligand (Table 3). Various phenyl
could also be tolerated under modified conditions sulfamates bearing both electron-donating and –
with higher temperature. To our delight, withdrawing functional groups afforded the
heteroaryl pivalate 1k reacted well to form the desired polyfluorobiphenyls in moderate yields.
corresponding product in 60% yield under
modified conditions with higher temperature. The electrophiles, we further investigated the
decarboxylative cross-coupling of other decarboxylative cross-coupling of potassium
Encouraged by our success on aryl C–O
potassium polyfluorobenzoates with 1a was also polyfluorobenzoates with benzylic pivalates
examined. Employing the modified reaction (Table 4).[13] By employing modified reaction
conditions with mixed solvent (toluene/DMA) conditions of aryl pivalates with higher
and higher temperature, the decarboxylative temperature, 2-naphthylmethyl pivalate 6a and 1-
cross-coupling of potassium tetrafluorobenzoate, naphthylmethyl pivalate 6b reacted well with
4-methyl
tetrafluorobenzoate
and potassium pentafluorobenzoates to furnish the
trifluorobenzoate with 1a furnished the desired polyfluorinated diarylmethanes in good
polyfluorobiaryls in satisfied yields. As to the yields. Similarly, 9-anthracenylmethyl pivalate 6c
reaction of potassium difluorobenzoate, low yield was also suitable substrate. The decarboxylative
of the desired product was obtained.
cross-coupling of potassium tetrafluorobenzoates
with 6a afforded the desired product in 62% yield
Table 3. Ni-catalyzed decarboxylative cross-coupling employing mixed solvent consisting toluene and
of potassium pentafluorobenzoates with aryl DMA.
sulfamates.a,b
Ni(cod)2 (10 mol%)
DPPF (10 mol%)
BINAP (10 mol%)
F
Table 4. Ni-catalyzed decarboxylative cross-coupling
of potassium polyfluorobenzoates with benzylic
pivalates.a, b
OSO2NMe2
COOK
F
F
F
F
F
+
F
F
Zn(OAc)2 (1.0 equiv)
chexane, 150 oC, 16 h
F
F
F
R
F
2a
COOK
R
Ni(cod)2 (10 mol%)
PCy3 (20 mol%)
Fn
4
5
OPiv
F
F
F
F
+
Ar
Ar
Fn
Zn(OAc)2 (1.0 equiv)
chexane, 190 oC, 16 h
F
F
F
F
F
F
F
F
6
2
7
F
F
F
F
F
F
F
F
F
F
F
tBu
Ph
F
F
F
F
5b 45%c
5c 63%c
5a 61%
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
7d 62%c
F3C
7a 72%
7c 68%
7b 65%
MeO
F
5d 41%c
5e 42%c
5f 46%c
a)
Reaction conditions: 4 (0.2 mmol), 2 (0.4 mmol),
Ni(cod)2 (0.02 mmol), PCy3 (0.04 mmol), Zn(OAc)2 (0.2
F
F
F
F
F
NC
F
MeO2C
F
c
o
b)
c)
mmol), hexane (3.0 mL), 190 C, 16 h. Isolated yield.
2b (0.6 mmol), toluene/DMA (2.0 mL/0.2 mL)
F
F
F
5h 51%c
5g 55%
a) Reaction conditions:
Ni(cod)2 (0.02 mmol), DPPF (0.02 mmol), BINAP
4 (0.2 mmol), 2a (0.4 mmol),
The synthetic versatility of this nickel-catalyzed
decarboxylative cross-coupling involving inert C–O
bond is demonstrated. As shown in Scheme 2, a range
of polyflurotriaryls could be synthesized from 6-
bromonaphthyl pivalate 8 via Suzuki coupling and
subsequent decarboxylative cross-coupling. In
c
(0.02 mmol), Zn(OAc)2 (0.2 mmol), hexane (3.0 mL),
150 oC, 16 h. b) Isolated yield. c) Ni(cod)2 (0.04 mmol),
DPPF (0.04 mmol), BINAP (0.04 mmol).
3
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10.1002/adsc.201800729
Advanced Synthesis & Catalysis
addition, two different polyfluorophenyl groups are
installed to 8 via sequential decarboxylative cross-
coupling reactions.
4
5
6
7
8
9
-
Zn(OAc)2
ZnCl2
59
9
-
-
Ag2CO3
Cu2O
10
7
PdCl2(PPh3)2
OPiv
-
K3PO4
OPiv
ArB(OH)2 (9)
Ni(cod)2/PCy3
Zn(OAc)2
61
toluene/H2O
90 oC, 16 h
F
10a R = H
10b R = OMe 82%
10c R = F 81%
76%
Br
8
R
NiCl2/PCy3
Zn(OAc)2
65
a) Reaction conditions: 2a (0.4 mmol), [Ni] (0.02 mmol),
F
F
Ni(cod)2/PCy3
c
PCy3 (0.04 mmol), [Additive] (0.2 mmol), hexane (3.0
Zn(OAc)2, 2a
mL), 170 C, 16 h. b) The yield was determined by GC, and
o
F
chexane
190 oC, 16 h
F
calibrated using ndodecane as internal standard.
11a R = H
62%
11b R = OMe 52%
R
F
F
75% (170 oC)
Ni(cod)2 (10 mol%)
PCy3 (20 mol%)
11c R = F
OPiv
OPiv
+
3a
Pd(OAc)2/PCy3
Zn(OAc)2, 2o
H
F
F
OPiv
Zn(OAc)2 (1.0 equiv)
chexane, 170 oC, 16 h
F
F
chexane
1a
14
Br
170 oC, 16 h
F
8
12 59%
F
Scheme 3. Reaction of 1a with 14 under standard
conditions.
F
F
Ni(cod)2/PCy3
Zn(OAc)2, 2a
F
F
chexane
190 oC, 16 h
F
On the basis of the above results and previous
reports,[3j], [14a], [15] we proposed a mechanism for
this decarboxylative cross-coupling (Scheme 4).
The oxidative addition of 2-naphthyl pivalate 1a
to the Ni0-PCy3 species generated the
13 61%
F
Scheme 2. Synthetic application
intermediate
step with intermediate II that was obtained via the
decarboxylation of potassium
pentafluorobenzoates 2a with the aid of Zn(OAc)2
afforded intermediate III The following
I. The subsequent transmetallation
Furthermore, the decarboxylation of 2a was
investigated to gain brief insights to the
mechanism of this decarboxylative cross-coupling
(Table 5).[3j], [3k], [14] Pentafluorobenzene 14 was
.
c
o
obtained in 9% yield in hexane at 170 C within
16 h while the adding of nickel catalysts like
Ni(cod)2 and NiCl2 or additives like ZnCl2,
Ag2CO3 and Cu2O gave similar results.
Remarkably, the adding of Zn(OAc)2 as additive
dramatically enhanced the decarboxylation of 2a
affording 14 in 59% yield while similar yields
were obtained employing the combination of
nickel catalysts and Zn(OAc)2. The results
obtained above indicated the crucial Zn(OAc)2
probably improves the reaction efficiency by
enhancing the decarboxylation step. In addition,
no 3a was obtained in the reaction of 1a with 14
under standard conditions, which ruled out the
possibility of this pathway (Scheme 3).
reductive elimination of III furnished the product
3a and regenerated the active Ni0 species.
Ni0Ln
3a
1a
F
F
F
F
Ni
Ln
F
Ni OPiv
Ln-2
I
III
MOPiv
Zn(OAc)2
CO2
FnAr
II
M
2a
Table 5. The Decarboxylation Reaction of 2a: Effects of
Reaction Parametersa.
Scheme 4. Proposed mechanism.
F
F
F
F
F
[Ni]/PCy3/[Additive]
F
COOK
F
H
In summary, the first nickel-catalyzed
decarboxylative cross-coupling of potassium
polyfluorobenzoates with unactivated phenol and
chexane, 170 oC, 16 h
F
F
F
2a
14
yield (%)b
phenylmethanol derivatives is disclosed.
A
entry
[Ni]/PCy3
-
[Additive]
variety of functional groups were tolerated, and
various polyfluorobiaryl and polyfluorinated
diarylmethanes were obtained in moderate to
1
2
3
-
-
-
9
7
Ni(cod)2/PCy3
NiCl2/PCy3
good
yields.
Remarkably,
preliminary
15
mechanistic studies indicated the effect of the
crucial Zn(OAc)2 might lie in the enhancement of
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800729
Advanced Synthesis & Catalysis
decarboxylation step. Additional exploration of
the substrate scope and mechanistic studies are
currently underway and will be reported in the
due course.
Wang, X.-H. Duan, Org. Biomol. Chem. 2016, 14,
7380-7391; m) P. Liu, G. Zhang, P. Sun, Org.
Biomol. Chem. 2016, 14, 10763-10777; n) B. R.
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Experimental Section
A 25-mL pressure tube equipped with a magnetic stirring
bar was dried with a heat-gun under reduced pressure and
filled with nitrogen after cooling to room temperature.
After adding aryl pivalate (0.2 mmol), and potassium
polyfluorobenzoate (0.4 mmol), the tube was introduced
inside a nitrogen-atmosphere glovebox. In the glovebox,
Ni(cod)2 (0.02 mmol, 5.6 mg), PCy3 (0.4 mmol, 11.2 mg)
and Zn(OAc)2 (0.2 mmol, 36.7 mg) were added to the tube,
which was sealed with O-ring tap and then taken out of the
glovebox. Then, cyclohexane (3.0 mL) was added to the
vessel under nitrogen atmosphere. The vessel was then
heated at 170 oC for 16 h in a heating module with stirring.
After that, the reaction mixture was cooled to room
temperature, filtered, concentrated and directly purified by
[3] a) L. J. Goossen, N. Rodriguez, C. Linder, J. Am. Chem.
Soc. 2008, 130, 15248-15249; b) L. J. Goossen, C.
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Commun. 2009, 7173-7175; c) L. J. Goossen, C. Linder,
N. Rodriguez, P. P. Lange, Chem. - Eur. J. 2009, 15,
9336-9349; d) L. J. Goossen, N. Rodriguez, P. P. Lange,
C. Linder, Angew. Chem., Int. Ed. 2010, 49, 1111-1114;
e) L. J. Goossen, P. P. Lange, N. Rodriguez, C. Linder,
Chem. - Eur. J. 2010, 16, 3906-3909; f) L. J. Goossen,
N. Rodriguez, C. Linder, P. P. Lange, A. Fromm,
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preparative
thin-layer
chromatography
(petroleum
ether/ethyl acetate as the eluent) to afford the product.
Acknowledgements
This work was supported by the grants from the National Natural
Science Foundation of China (21602096) and Nanchang
University (06301425).
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6
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10.1002/adsc.201800729
Advanced Synthesis & Catalysis
COMMUNICATION
Nickel-Catalyzed Decarboxylative Cross-Coupling
of Potassium Polyfluorobenzoates with
Unactivated Phenol and Phenylmethanol
Derivatives
Ni(cod)2
PCy3
Ar
Fn
Ar
OR
+
KOOC
Fn
Adv. Synth. Catal. Year, Volume, Page – Page
Zn(OAc)2
"Crucial Role"
OR
R = COtBu, SO2NMe2
Fn
Ar
Ar
Quan Chen,+ Aizhen Wu,+ Shengxiang Qin, Meiqi
Zeng, Zhiping Le,* Zhaohua Yan,* Hua Zhang*
7
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